Search Results (30)

Background/Objectives: Heterofunctional cationic polyester dendrimers derived from a 2-(bromomethyl)-2-(hydroxymethyl)propane-1,3-diol (BHP-diol) based AB₂C monomer were evaluated as efficient and biodegradable nonviral carriers for siRNA delivery. Methods: These dendrimers feature dual internal and external charge architectures, enabling precise control of charge distribution and siRNA interaction strength. Results: They achieved complete siRNA complexation at nitrogen-to-phosphate (N/P) ratios of 0.50–2.14 and provided up to 93% RNase protection, outperforming amino-functional scaffolds based on 2,2-bis(methylol)propionic acid (bis-MPA). In human (T98G) and murine (GL261) glioblastoma cells, the dendrimers exhibited minimal cytotoxicity while achieving 52–61% target protein knockdown, a two- to three-fold improvement over conventional polyester dendrimers, and approaching the silencing efficiency of the commercial Interferin^® reagent. Conclusions: The combination of high complexation efficiency, strong nuclease resistance, and excellent biocompatibility establishes these heterofunctional dendrimers as a new generation of precisely tunable, biodegradable vectors for therapeutic siRNA delivery. Full article

This study outlines a method for preparing a complex involving glycoluril and melamine (GU-ME). The structure of the resultant complex was analyzed using IR and NMR spectroscopy. In the subsequent phase, the polymer GUMEFA was derived from the resultant complex, employing hydroxyethylidene diphosphonic acid (HEDP) as a sustainable plasticizer, with a proposed chemical mechanism for its formation. The molecular weight of the resulting GUMEFA was analyzed, and the formation chemistry was proposed. GUMEFA was characterized, and its free formaldehyde and methylol group contents were investigated. It was observed that GUMEFA prepared with HEDP contained approximately 1.15–1.34 wt.% free formaldehyde and 1.56–0.54 wt.% methylol groups. These findings provide valuable insights for developing resins of different compositions and applications, thereby paving the way for producing composite materials with tailored properties. Full article

Phenol–formaldehyde (PF) resins remain the preferred adhesive for exterior plywood, as they confer these boards their extreme weather resistance. However, their high price and toxicity has made phenol alternatives, such as technical lignins, increasingly more attractive. While many works report the use of kraft lignin, the most commercially available form are lignosulphonates (LS). However, these lack industrial success and are associated with low moisture resistance. In the current study, lignosulphonate–phenol–formaldehyde (LPF) resoles were synthesized considering a phenol replacement of 30% (w/w). Two LS samples of softwood (SLS) and hardwood (HLS) origin were compared. These samples were previously methylolated to increase their reactivity. The effectiveness of the treatment was confirmed through the Automated Bonding Evaluation System. Plywood was manufactured and tested according to EN 314 class 3 for exterior conditions, which is seldom found in the literature. Although a 35% increase in shear strength is still necessary to comply with the standard, methylolated SLS was the most promising substitute, as it resulted in the highest board performance. Notably, when this sample was used without previous methylolation, the plywood boards suffered delamination during immersion in boiling water prior to shear testing. These results reinforce the need for the methylolation of LS to increase the weather resistance of plywood. Full article

Nitrogen (N) is the essential plant nutrient needed by turfgrass in the greatest quantity. Urea and urea-based liquids are arguably the safest, least expensive, and subsequently most popular soluble N fertilizers. Unfortunately, urea fertilizer application to turfgrass is often subject to NH₃ volatilization: a deleterious phenomenon from both environmental and agronomic perspectives. The objective of this research was to quantify the efficacy of creeping bentgrass (Agrostis stolonifera L.) golf course fairway foliar fertilization by urea-based N fertilizers as influenced by a petroleum-derived spray oil (PDSO) containing Cu II phthalocyanine colorant (Civitas Turf Defense^TM Pre-M1xed, Intelligro LLC, Mississauga, ON, Canada). In 2019 and 2020, a maintained creeping bentgrass fairway received semimonthly 9.76 kg ha^–1 soluble N treatment either alone or in combination with Civitas at a rate of 27 L ha^–1. In the 48 h following foliar application, fertilizer N loss as NH₃ ranged from 1.3 to 5.5% and corresponded directly to fertilizer urea content but not Civitas inclusion. In the 1 to 14 d following semimonthly treatment, Civitas had either a beneficial (methylol urea and UAN) or negligible (urea) effect on canopy mean dark green color index. Once cumulative N inputs exceeded 47 kg ha^–1, creeping bentgrass fairway shoot growth and N nutrition were consistently increased by Civitas complementation of commercial liquid N fertilizer. Over the 2-yr study, absolute mean percent fertilizer N recovery from plots treated by Civitas-complemented foliar liquid N treatment exceeded their ’N only’ counterparts by 8.7%. Full article

In the present work, the new N-methylol and O-alkyl derivatives of 4,5-dihydroxyimidazolidine-2-thione (DHIT) are synthesized. The effects of N-alkyl, N-phenyl, N-methylol, and O-alkyl substituents of DHIT on the ¹³C and ¹H signals in NMR spectra of the imidazolidine-2-thione ring are systematized using quantum chemical calculations. The shift values of carbon and hydrogen atoms are specific for the geometric isomers of the indicated DHIT derivatives. The chemical shifts of the carbon atoms of the methine groups allows for identifying the cis and trans isomers of the N-alkyl derivatives of DHIT due to the up-field shifts of the cis isomers. The introduction of an alkyl substituent at the N-position of the imidazolidine-2-thione ring leads to the up-field shifts of the carbon atoms of the ring due to the inductive effects of these groups. The ring current effect in the N-phenyl derivatives of DHIT that affects the positions of the carbon signals of the imidazolidine-2-thione ring has been found. The N-methylol derivatives of 4,5-dihydroxyimidazolidine-2-thione have been identified for the first time using 1D and 2D NMR. Full article

Out of the 50 to 70 million tons of lignin that are produced annually, only 1 to 2% are used for value-added products. Currently, 90% of the total market of this compound corresponds to lignosulphonates (LS). The most successful industrial attempts to use lignin for wood adhesives rely on using it as a partial substitute in phenol–formaldehyde or urea–formaldehyde resins. However, lignin’s aromatic ring presents a low number of reactive sites. Several methods have been proposed to improve its reactivity, such as prior methylolation with formaldehyde. Off-line methods are commonly applied to monitor this reaction’s progress, but this introduces a significant delay in the analysis. This study proposes a new method for in-line monitoring of the methylolation reaction using visible spectroscopy. In order to monitor the reaction progress, principal component analysis was applied to the spectra, and the obtained scores were analyzed. When these results were plotted against those obtained by the off-line methods, a satisfactory regression was obtained at 50 °C (R² = 0.97) and 60 °C (R² = 0.98) for two different LS samples. Therefore, it was concluded that visible spectroscopy is a promising technique for studying lignin methylolation. Full article

The properties of solvent-based pressure-sensitive adhesive (PSA) acrylics, especially shrinkage, are mostly determined by the type and amount of the crosslinking agent added to the prepolymer or by the crosslinking method. The shrinkage profiles of the selected solvent-based acrylic PSA coated on PVC film were investigated using metal chelates (between 0 and 0.55 wt.%), N-methylol acrylamide (up to 8 wt.%), polycarbodiimide and amino resins (up to 6 wt.%), diisocyanate (up to 1 wt.%), multi-functional propylene imines (up to 0.9 wt.%), conventional photoinitiators (up to 3 wt.%) and copolymerizable photoinitiators (up to 2 wt.%). These chemicals were both crosslinking agents that react after the solvent has been evaporated or at higher temperatures, and to the crosslinking agents that react under UV radiation. Some of them were copolymerizable, and others were added to the prepolymer before crosslinking. The best results of shrinkage (0.2%) were obtained by using the UV-crosslinking method and copolymerizable photoinitiators ZLI 3331 and ABP, as well as metal chelates AlACA and TiACA and multifunctional propylene imine Neocryl CX-100 (0.2%). Acceptable results were also achieved for amide BPIA (0.3%), benzophenone derivative PCB (0.4%), N-methylol acrylamide (0.35%) and benzoguanamine resin Cymel 1123 (0.45%). Full article

The aim of the present research work was to develop halogen and formaldehyde-free, durable flame retardant fabric along with multifunctional properties and to find the optimal conditions and parameters. In this research, zinc oxide nanoparticles (ZnO NPs) were grown onto 100% cotton fabric using the sonochemical method. Zinc acetate dihydrate (Zn(CH₃COO)₂·2H₂O) and sodium hydroxide (NaOH) were used as precursors. After ZnO NPs growth, N-Methylol dimethylphosphonopropionamide (MDPA) flame retardant was applied in the presence of 1, 2, 3, 4-butanetetracarboxylic acid (BTCA) as cross-linkers using the conventional pad–dry–cure method. Induced coupled plasma atomic emission spectroscopy (ICP-AES) was used to determine the deposited amount of Zn and phosphorous (P) contents. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR) were employed to determine the surface morphology and characterization of the developed samples. Furthermore, the thermal degradation of the untreated and treated samples was investigated by thermogravimetric analysis (TGA). Furthermore, the vertical flame retardant test, limiting oxygen index (LOI), ultraviolet protection factor (UPF), and antibacterial activity of samples were examined. The developed samples showed excellent results for flame retardancy (i.e., 39 mm char length, 0 s after flame time, 0 s after glow time), 32.2 LOI, 143.76 UPF, and 100% antibacterial activity. Full article

Biodiesel has been established as a promising alternative fuel to petroleum diesel. This study offers a promising energy conversion platform to valorise high acidity waste cooking oil (WCO) into biodiesel in a single-step reaction via supercritical methanol. Carbon dioxide (CO₂) has been used as a co-solvent in the reaction with a catalytic effect to enhance the production of biodiesel. This work provides an in-depth assessment of the yield of four fatty acids methyl esters (FAME) from their correspondent triglycerides and fatty acids. The effects of four independent process variables, i.e., methanol to oil (M:O) molar ratio, temperature, pressure, and time, have been investigated using Response Surface Methodology (RSM). Four quadratic models have been developed between process variables and the yield of FAMEs. The statistical validation of the predicted models has been performed using analysis of variance (ANOVA). Numerical optimisation has been employed to predict the optimal conditions for biodiesel production. The predicted optimal conditions are at 25:1 M:O molar ratio, 254.7 °C, 110 bar within 17 min resulting in 99.2%, 99.3%, 99.13%, and 99.05% of methyl-oleate, methyl-palmitate, methyl-linoleate, and methyl-stearate yields, respectively. The predicted optimum conditions have been validated experimentally. Full article

The excess biomass of drifting algae and their casting to the Baltic Sea coast imposes a significant environmental burden. The analysis of beach-cast algae showed that the dominant species are macroalgae Ulva sp., Furcellaria lumbricalis, Cladophora sp., and Polysiphonia fucoides. The biomass of Furcellaria and Polysiphonia algae, containing 25.6% and 19.98% sugars, respectively, has the greatest resource potential in terms of obtaining carbohydrates. Fucose, glucose, and galactose were found to be the most common carbohydrates. The lipid content did not exceed 4.3% (2.3–4.3%), while the fatty acid composition was represented by saturated fatty acids (palmitic, stearic, methyloleic, behenic, etc.). The highest content of crude protein was found in samples of macroalgae of the genus Polysiphonia and amounted to 28.2%. A study of the elemental composition of drifting algae revealed that they have a high carbon content (31.3–37.5%) and a low hydrogen (4.96–5.82%), and sulfur (1.75–3.00%) content. Red algal biomass has the most resource potential in terms of biofuel generation, as it has a high number of lipids and proteins that can produce melanoidins during hydrothermal liquefaction, enhancing the fuel yield. The study noted the feasibility of using the biomass of the studied algae taxa to produce polysaccharides and biofuels. The analyses of antioxidant properties, fat content, and fat composition do not provide convincing evidence of the viability of using the aforementioned macroalgae for their production. Full article

A TiO₂ nanoparticle-loaded polymer fiber web was developed as a functional material with the ability to adsorb and photo-catalytically degrade organic pollutants in aquatic media. A linear copolymer of N-isopropylacrylamide (primary component) and N-methylol acrylamide (poly(NIPA-co-NMA)) was prepared, and composite fibers were fabricated by electrospinning a methanol suspension containing the copolymer and commercially available TiO₂ nanoparticles. The crosslinking of the polymer via the formation of methylene bridges between NMA units was accomplished by heating, and the fiber morphology was analyzed by electron microscopy. 4-Isopropylphenol generated by the degradation of bisphenol A—one of the endocrine-disrupting chemicals—was used as the model organic pollutant. As poly(NIPA) is a thermosensitive polymer that undergoes hydrophilic/hydrophobic transition in water, the temperature-dependence of the adsorption and photocatalytic degradation of 4-isopropylphenol was investigated. The degradation rate was analyzed using a pseudo-first-order kinetic model to obtain the apparent reaction rate constant, k_app. The enhancement of the photocatalytic degradation rate owing to the adsorption of 4-isopropylphenol onto thermosensitive poly(NIPA)-based fibers is discussed in terms of the ratio of the k_app of the composite fiber to that of unsupported TiO₂ nanoparticles. Based on the results, an eco-friendly wastewater treatment process involving periodically alternated adsorption and photocatalytic degradation is proposed. Full article

Low cost and favorable handling characteristics make urea (46-0-0) a leading nitrogen source for frequent, foliar N fertilization of golf course putting greens in season. Yet few field investigations of resulting NH₃ volatilization from putting greens have been directed. Meanwhile, NH₃ emissions degrade air and surface water quality. Our objective was to quantify NH₃ volatilization following practical, low-N rate, and foliar application of commercial urea-N fertilizers. Over the 2019 and 2020 growing seasons in University Park, PA, USA, an industrial vacuum pump, H₃BO₃ scrubbing flasks, and sixteen dynamic flux chambers were employed in four unique experiments to measure NH₃ volatilization from creeping bentgrass putting greens (Agrostis stolonifera L. ‘Penn G2’) in the 24 h period ensuing foliar application of urea based-N at a 7.32 or 9.76 kg/ha rate. Simultaneous and replicated flux chamber trapping efficiency trials showing 35% mean NH₃ recovery were used to adjust NH₃ volatilization rates from treated plots. Under the duration and conditions described, 3.1 to 8.0% of conventional urea N volatilized from the putting greens as NH₃. Conversely, 0.7 to 1.1% of methylol urea liquid fertilizer (60% short-chain methylene urea) or 0.7 to 2.2% of urea complimented with dicyandiamide (DCD) and N-(n-butyl) thiophosphoric triamide (NBPT) volatilized as NH₃. Full article

To investigate the effects of lignin methylolation and lignin adding stage on the resulted lignin-based phenolic adhesives, Alcell lignin activated with NaOH (AL) or methylolation (ML) was integrated into the phenolic adhesives system by replacing phenol at various adhesive synthesis stages or directly co-polymerizing with phenolic adhesives. Lignin integration into phenolic adhesives greatly increased the viscosity of the resultant adhesives, regardless of lignin methylolation or adding stage. ML introduction at the second stage of adhesive synthesis led to much bigger viscosity than ML or AL introduction into phenolic adhesives at any other stages. Lignin methylolation and lignin adding stage did not affect the thermal stability of lignin based phenolic adhesives, even though lignin-based adhesives were less thermally stable than NPF. Typical three-stage degradation characteristics were also observed on all the lignin-based phenolic adhesives. Three-ply plywoods can be successfully laminated with lignin based adhesives, and it was interesting that after 3 h of cooking in boiling water, the plywoods specimens bonded with lignin-based phenolic adhesives displayed higher bonding strength than the corresponding dry strength obtained after direct conditioning at 20 °C and 65% RH. Compared with NPF, lignin introduction significantly reduced the bonding strength of lignin based phenolic adhesives when applied for plywood lamination. However, no significant variation of bonding strength was detected among the lignin based phenolic adhesives, regardless of lignin methylolation or adding stages. Full article

Melamine-formaldehyde (MF) resins are widely used as surface finishes for engineered wood-based panels in decorative laminates. Since no additional glue is applied in lamination, the overall residual curing capacity of MF resins is of great technological importance. Residual curing capacity is measured by differential scanning calorimetry (DSC) as the exothermic curing enthalpy integral of the liquid resin. After resin synthesis is completed, the resulting pre-polymer has a defined chemical structure with a corresponding residual curing capacity. Predicting the residual curing capacity of a resin batch already at an early stage during synthesis would enable corrective measures to be taken by making adjustments while synthesis is still in progress. Thereby, discarding faulty batches could be avoided. Here, by using a batch modelling approach, it is demonstrated how quantitative predictions of MF residual curing capacity can be derived from inline Fourier Transform infrared (FTIR) spectra recorded during resin synthesis using partial least squares regression. Not only is there a strong correlation (R² = 0.89) between the infrared spectra measured at the end of MF resin synthesis and the residual curing capacity. The inline reaction spectra obtained already at the point of complete dissolution of melamine upon methylolation during the initial stage of resin synthesis are also well suited for predicting final curing performance of the resin. Based on these IR spectra, a valid regression model (R² = 0.85) can be established using information obtained at a very early stage of MF resin synthesis. Full article