Acrylic Acid Research Articles

Stabilizing the Bilateral Interfaces by a PVDF-Based Double-Layer Solid Composite Electrolyte with a Relieved Dehydrofluorination Effect for Solid-State Lithium Metal Batteries.

The dehydrofluorination effect of poly(vinylidene fluoride) (PVDF) induced by ceramic fillers with an alkaline surface compromises the comprehensive properties of the solid composite electrolyte (SCE) and leads to the deficient performance of the solid-state lithium metal batteries (SLMBs). In this work, a unique PVDF-based double-layer solid electrolyte was fabricated, which consisted of a Li6.4La3Zr1.4Ta0.6O12 (LLZTO)-filled SCE with poly(acrylic acid) (PAA) as an alkalinity-scavenging agent in contact with the Li anode, and another SCE with lithium difluoro(oxalato)borate (LiDFOB) as a film-formation additive facing the cathode. It is found that a moderate amount of PAA relieves the dehydrofluorination degree of the PVDF matrix and improves the Li plating/stripping reversibility, and the addition of LiDFOB is involved in the formation of a stable passivation film on the cathode. Consequently, the resultant double-layer SCE holds favorable overall properties, especially being well-compatible with both electrodes, endowing the SLMBs with superior cycle and rate performance at room temperature.

Ligand content and driving force effects on ion-ion permselectivity in ligand-functionalized membranes

Ion-selective membranes could enable sustainable critical material separations processes because of their scalability, low energy consumption, and low chemical input. The effects of membrane water content and incorporation of ion-coordinating ligands have been studied via computation and experiment to develop structure-performance relationships. However, few studies systematically investigate the effects of membrane composition beyond monomer chemical identity or the balance of driving forces such as diffusion and electromigration. Here we synthesized a library of poly(ethylene glycol) acrylate membranes with varying percentages of ion-coordinating monomers (acrylic acid, 4-vinylpyridine) to investigate the influence of ligand content on cation permeabilities and permselectivities. Trends in membrane performance under electrodialysis and diffusion were compared to elucidate the relative effects of separation driving forces and to inform electrochemical operation. We observed order-of-magnitude permeability reductions with ligand content for ions capable of multidentate ligand complexation, especially for nickel in the pyridine-containing membranes. As a result, lithium/nickel permselectivity gradually increased by a factor of 1.65 × from 10 to 50 mol% pyridine membranes. We further demonstrated simultaneous improvements in lithium/nickel separation productivity (1.75 ×) and selectivity (2.99 ×) with increasing electric potential driving force. Ultimately, results from this study provide design insights for ligand-functionalized membranes in electrified ion-ion separations processes.

Synthesis and Characterization of cellulose-derived superabsorbent hydrogel and its applications in the treatment of wastewater containing heavy metal ions

A cellulose xanthate (CX) based polymer hydrogel has been synthesized using free radical graft polymerization technique. Two monomers Acrylic Acid (AA) and Acrylonitrile (AN) were reacted with cellulose xanthate to synthesize the desired hydrogel CX-g-poly(AA-co-AN). The synthesized hydrogel has been characterized by various techniques viz. Thermo-gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), UV-visible spectroscopy (UV), Field emission scanning electron microscope (FESEM) and Point zero charge (PZC). This hydrogel has been employed for the removal of toxic metal ions from wastewater. The maximum percentage removal has been found to be 97.5 (±4.87)% for Cu2+ ions and 96.1 (±4.80)% for Co2+ ions under optimum pH 6. The calculated adsorption capacities have been found to be 330.03 (±35.3) mg/g for Cu2+ ions and 325.73 (±22.4) mg/g for Co2+ ions using the Langmuir Adsorption isotherm model. The thermodynamic parameters depicted that the process was endothermic, and spontaneous. The adsorption kinetics data shows excellent fit with pseudo-second-order kinetic model. The synthesized hydrogel exhibits a high swelling ratio of 846.85 (±42.36) g/g and retention ratio of 50.12 (±2.50) % in distilled water. Also, the synthesized hydrogel showed good reusability, exhibiting percentage removal 83.2% for Cu2+ ions and 81.3% for Co2+ ions in the fifth cycle.

Utilizing acrylic acid polymer hydrogel for 3-D quality assurance in CyberKnife radiotherapy

Dosimetry tools play a crucial role in radiotherapy as they are essential for recording and validating intricate 3-D dose distributions. This research introduces and examines a novel acrylic acid polymer hydrogel (ACAPHG) dosimeter composition designed for 3-D dose verification and quality assurance in the context of radiotherapy treatment. A phantom made of an 80 mm diameter cylindrical glass container was utilized. The phantom contained the hydrogel, which served as the medium for radiation exposure. The water equivalent hydrogel within the phantom was subjected to irradiation by a CyberKnife robotic radiotherapy system. An optical computed tomography (OCT) scanner with sub-millimeter resolution was used to obtain imaging data. The dose distribution of a CyberKnife robotic SRS/SBRT treatment plan for a brain cancer patient was compared to that of the hydrogel's OCT scan using 2-D and 3-D gamma analysis with a criterion of 3% dose difference and 3 mm distance-to-agreement. A gamma pass rate of 94.1% for the 2-D gamma analysis and a pass rate of 99% for the 3-D gamma analysis were calculated within the region at which the treatment planning system data drops to 20% of the maximum dose. The use of the ACAPHG dosimeter in conjunction with the described setup suggests that it has the potential to offer an accurate 3-D verification of complex dose distributions in SRS/SBRT radiotherapy treatments. By employing the ACAPHG dosimeter and utilizing OCT scanning, this dosimeter enables the assessment and validation of intricate dose distributions in these advanced radiotherapy treatments.

Tissue-Compatible and Lubricated Hydrogel Catheter with Promising Activity Against Polymicrobial Infections for Ventilator-Associated Pneumonia Prevention.

Endotracheal intubation is a vital means of saving critically ill patients. However, the inserted catheter often causes tissue damage and the formation of tenacious biofilms containing drug-resistant bacteria and fungi, leading to severe ventilator-associated pneumonia (VAP). Currently, the resolution of VAP is usually based on antibiotic treatment and lacks targeted prophylaxis. Here, a quaternary phosphonium salts functionalized hydrogel catheter that enhances tissue compatibility yet inhibits complex and tenacious pathogens in the catheter, thus preventing VAP is reported. By copolymerizing the quaternary phosphonium electrolyte and acrylic acid monomers, the hydrogel catheter demonstrates good shape-supporting ability, and its strength and modulus can be adjusted over a wide range to meet the needs of different ages. Moreover, it possesses good tissue compatibility, antifouling properties, stable lubrication capability, and superior hydrophilicity, which may mitigate tissue damage caused by contact. Importantly, the hydrogel catheter demonstrates potent broad-spectrum intrinsic antimicrobial activity, eradicating nearly 99% of multi-drug resistant bacteria and 80% of fungi. To validate its role in preventing VAP, the real VAP pathogenesis process is mimicked, establishing a polymicrobial infections model considering time effects. The results prove that the hydrogel catheter effectively inhibits the invasion of various drug-resistant pathogens and prevents biofilm formation.

Preparation and performance evaluation of a low‐damage fracturing fluid for unconventional reservoirs

AbstractThe characteristics of tight matrix, underdeveloped natural fractures, small pore throat radius, poor pore connectivity, and abundant clay minerals result in a high potential for damage to the tight sandstone reservoirs of the Shaximiao Formation in the Qiulin Block in the Sichuan Basin. In order to reduce the retention damage caused by fracturing fluid to the tight sandstone reservoir, a low damage fracturing fluid system applicable to the target reservoir is developed in this work, and the indoor performance meets the requirements of on‐site fracturing operation. A low‐damage, heat‐resistant, shear‐stable amphiphilic polyacrylamide (PAAD) was prepared by free radical polymerization in aqueous solution using acrylamide, acrylic acid, and methacryloyloyloxyethyl dimethyloctadecyl ammonium bromide (DM18) as the monomers. The amphoteric polyacrylamide was characterized by Fourier infrared spectroscopy, nuclear magnetic resonance spectroscopy (1H NMR), light scattering molecular weight determination, and thermogravimetric analysis. Fracturing fluids were formulated with the amphiphilic hydrophobic associative polymer PAAD as a drag‐reducing agent, the fluorine‐containing and nonionic complex surfactant FD1 as a clean‐up additive, CT10‐4B as a bactericide and CT1‐12 as an emulsion breaker. The fracturing fluid formulation was preferred, and the performance of the fracturing fluid was evaluated in terms of temperature resistance and shear resistance, drag reduction, anti‐expansion, and core damage. The fracturing fluid showed good temperature and shear resistance, with a viscosity retention of 58.4% at 120°C and 170 s−1 shear for 1 h. At a loading of 0.1%, the drag reduction rate reaches 72.3%, the anti‐expansion rate of the gel‐breaking fluid is 86.04%, and the damage rate to the tight sandstone core is 16.25%. The results show that the fracturing fluid has good heat resistance and shear stability, as well as low damage and good resistance reduction and anti‐expansion properties. This work can provide new strategies for designing polymeric fracturing fluids with low damage, good heat resistance and shear stability.

Accelerated Nanocomposite Hydrogel Gelation Times Independent of Gold Nanoparticle Ligand Functionality.

The expansive use of hydrogels in healthcare relies on carefully tuned properties in dynamic environments with predictable behavior, including time sensitive biological systems and biomedical applications. To meet demands in these settings, nanomaterials are often introduced to a hydrogel matrix which simultaneously elevates potential applications while adding complexity to fundamental characteristics. With respect to drug delivery, gold nanoparticles have modifiable surfaces to carry an array of targeted drug treatments. However, different molecules acting as capping ligands possess different chemical structures that can impact gelation times. To understand the influence of capping ligand chemistry on polyacrylamide (PAM) based nanocomposite hydrogel radical gelation time, gold nanoparticle (Au NP) capping ligands were selected to encompass varying functional groups and molecular weights: citrate, cetyltrimethylammonium bromide, polyvinylpyrrolidone, and poly(acrylic acid). Gelation times were quantified as the storage-loss moduli crossover point in rheological time sweeps at constant strain and frequency. The dominating factor for gelation time was the presence of Au NPs, independent of a diverse range of capping ligand structures. The gelation times were also markedly faster than the same capping ligand structures used as stand-alone molecular additives. The accelerated Au NP gelation times, under 2 min, are attributed to the Au NPs acting as a cross-linker, promoting gelation. These results bolster the potential implementation of Au NP nanocomposite hydrogels in time-sensitive biomedical applications as robust drug carriers.

High-performance hydrogel membranes with superior environmental stability for harvesting osmotic energy

A collection of innovative nanofluidic systems has been developed to harness Gibbs free energy and convert it into osmotic energy. Nevertheless, these systems frequently encounter challenges such as low output power density, inadequate mechanical stability, and diminished performance in extreme conditions. In this work, we utilized a simple thermal polymerization method to fabricate a charged phytic acid (PA)–acrylic acid (AA)–3-sulfopropyl acrylate potassium salt (SPAK) hydrogel (PASH) membrane with anti-drying and anti-freezing properties, alongside mechanical stability. Using a silicon window with a testing area of 3 × 10−8 m2, a high power density of 30.94 W/m2 was achieved in artificial seawater and river water environments (0.5/0.01 M NaCl). Notably, an even higher power density of 103.9 W/m2 was attained in artificial saline lake and river water environments (5/0.01 M NaCl). Meanwhile, the PASH membrane demonstrated outstanding performance in low temperatures and various acidic and alkaline environments, offering the potential for osmotic power generation in extreme conditions. This work provides essential theoretical foundations and experimental evidence for the development of sustainable osmotic energy conversion technologies, contributing to the advancement and innovation in the field of blue osmotic energy.

Synthesis and characterization of guar gum xanthate derivative super adsorbent hydrogel for the capturing of heavy metal ions from wastewater

The Guar Gum Xanthate based hydrogel GGmX-g-poly(AA-co-HEMA) has been successfully synthesized by using the graft copolymerization of two monomers, acrylic acid (AA) and 2-hydroxyethyl methacrylate (HEMA) hydrogel. The synthesis follows the free-radical graft polymerization method. UV-visible spectroscopy (UV), Thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), Point zero charge (PZC), and field emission scanning electron microscopy (FESEM) were employed for the characterization of the synthesized hydrogel. This hydrogel has shown a high swelling ratio of 430.2 g/g and retention of 75.82% in distilled water which is a notable result. By using GGmX-g-poly(AA-co-HEMA) hydrogel, the maximum percentage of heavy metal ions removal from wastewater was found to be 98.5(±1.5)% and 97.1(±1.5) at optimum pH 6 and 6.5 for Cu2+ and Ni2+ solutions respectively. The Langmuir adsorption isotherm fits best for the adsorption data indicating a monolayer adsorption with maximum adsorption capacity of 423.72 (±26.1) mg/g and 404.85 (±31.4) mg/g for Cu2+ and Ni2+ ions respectively. The pseudo-second-order kinetic model provides the most accurate depiction of adsorption kinetics with rate constant 9.1 × 10−4 (±1.37×10−4)g/(mg.min) for Cu2+ and 8.3 × 10−4 (±1.24×10−4)g/(mg.min) for Ni2+ ions, respectively. The negative ΔG value (-4.75 kJ/mol for Cu2+ and −3.26 kJ/mol for Ni2+ ions) and positive value of ΔH (57.55 (±5.41) kJ/mol for Cu2+ and 40.60(±5.37) kJ/mol for Ni2+ ions) suggested the process to be spontaneous, endothermic, and feasible. It has been found that the hydrogel has excellent regenerative capacity with the % adsorption has been found to be 84.8% for Cu2+ and 82.4% for Ni2+ ions for the fifth cycle.

Intestinal distribution of anionic, cationic, and neutral polymer-stabilized nanocarriers measured with a lanthanide (europium) tracer assay

Nanocarriers, more commonly called nanoparticles (NPs), have found increasing use as delivery vehicles which increase the oral bioavailability of poorly water-soluble and peptide therapeutics. Therapeutic bioavailability is commonly assessed by measuring plasma concentrations that reflect the absorption kinetics. This bioavailability is a convolution of the gastrointestinal distribution of the NP vehicle, the release rate of the encapsulated therapeutic cargo, and the absorption-metabolism-distribution kinetics of the released therapeutic. The spatiotemporal distribution of the NP vehicle in the gastrointestinal tract is not well studied and is a buried parameter in PK studies used to measure the effectiveness of an NP formulation. This work is a study of the intestinal distribution and fate of orally dosed NPs in male CD-1 mice over 24 h. NPs have identical hydrophobic cores – composed of poly(styrene) homopolymer, a naphthalocyanine dye, and oleate-coated europium oxide colloids – with one of four different surface stabilizers: neutral poly(styrene)-block-poly(ethylene glycol) (PS-b-PEG), moderately negative hydroxypropyl methylcellulose acetate succinate (HPMCAS), highly negative poly(styrene)-block-poly(acrylic acid) (PS-b-PAA), and highly cationic adsorbed chitosan HCl on PS-b-PAA stabilized NPs. NP hydrodynamic diameters are all below 200 nm, with some variation attributable to the molecular properties of the stabilizing polymer. The encapsulated hydrophobic europium oxide colloids do not release soluble europium ions, enabling the use of highly sensitive inductively coupled plasma mass spectrometry (ICP-MS) to detect NP concentrations in digested biological tissues.Highly anionically-charged PAA and cationically-charged chitosan stabilized NPs showed statistically significant increased retention compared to the neutral PEG-stabilized NPs at p < 0.05 significance and (1-β) > 0.95 power. HPMCAS-stabilized NPs showed statistically insignificant greater retention than PEG-stabilized NPs, and all NP formulations showed clearance from the intestines within 24 h. Different surface charges preferentially reside in different segments of the intestines, where cationic chitosan-stabilized NPs showed increased retention in the small intestines (ileum) and anionic PAA-stabilized NPs in the large intestines (caecum and colon). Modifying the surface charge of a NP can be used to modulate mucoadhesion, total retention, and intestinal segment specific retention, which enables the rational design of delivery vehicles that maximize residence times in appropriate locations.

Enhancing electrochemical reductive defluorination of PFASs using ZIF-67 modified cathode: Mechanistic insights and performance optimization

The effectiveness of electrochemical reductive defluorination is impeded by the low environmental concentrations of per- and polyfluoroalkyl substances (PFASs) and the robust nature of C − F bonds. In this work, we investigate the zeolitic imidazolate framework-67 (ZIF-67) as a promising catalyst for PFASs remediation. We show that ZIF-67 hold promise for simultaneous adsorption and reductive defluorination of 2-(trifluoromethyl) acrylic acid (TFMAA). Following a 48-hour treatment, the ZIF-67 modification significantly improves the adsorption of TFMAA onto the cathode surface, achieving removal and defluorination efficiencies of 99.66 % and 97.16 %, respectively (C0 = 5 mg L−1, applied voltage of −1.2 V vs. Ag/AgCl). Furthermore, the atomic H*, catalyzed by the Co−N4 structure, boosts the reductive defluorination of TFMAA through indirect mechanisms, while the nitrogen loss due to carbonization further enhances the catalytic defluorination efficiency. This research presents a novel electrode material for PFASs defluorination and offers mechanistic insights into the defluorination process.

Thermally stimulated bio-acrylate based detachable adhesives with sustainable bonding-debonding design

The electronics and automotive industries utilize acrylic adhesives extensively. Their exceptional mechanical strength, accompanied by their permanent nature, renders recycling impracticable. Present work has successfully synthesized acrylate biopolymer based detachable adhesive, which is both eco-friendly and sustainable. Glycerol, from mustard oil, was oxidatively-dehydrated to synthesize acrylic acid, which along with dimethyl glyoxime was chain polymerized to obtain an eco-friendly acrylic based hot melt detachable adhesive (AAHMDA). Mechanical strength of prepared adhesive was tested through thermo-mechanical bonding-debonding cycles on glass, wood, and metal. In three tests of 0.2 g adhesive against specific applied stress on all surfaces, metal (1494.49 N/m2) and wood (1851.17 N/m2) remained intact for 2 h and 30 min. Maximum cleavage stress (applied weight) on glass, wood, and metal slides, using 0.2 g adhesive, was found to be 26503.61 N/m2 (1200 g), 19824.71 N/m2 (950 g), and 26328.24 N/m2 (1300 g), respectively, when repeatedly tested for 15 cycles. Gel contents and water absorption capacity of sample were found at 99.79 % and 38.78 %, respectively. Prepared AAHMDA possesses the capability to create a robust mechanical bond that is readily detachable when heated, which makes it a cost effective adhesive. Owing to its strong bonding and simple detachment procedure, AAHMDA appears to have a promising future in materials research, sustainability initiatives, and changing industry demands.

Synthesis and characterization of allyl mannitol cross-linker based novel hydrogel for capturing of toxic metal ions from aqueous solution

ABSTRACT Three grades of allyl-mannitol cross-linker-based hydrogel (AMCLHs hydrogel) have been synthesized with the help of acrylic acid and acrylamide monomers using a free radical co-polymerization technique. The three prepared grades of AMCLHs hydrogel have been referred to as AMCLHs-1, AMCLHs-2, and AMCLHs-3, respectively. The prepared AMCLHs hydrogels have been characterized by several analytical techniques viz. Fourier transform infrared (FTIR) spectroscopy, thermogravimetric (TG) analysis, point of zero charge (ΔpHPZC), analysis, and scanning electron microscope (SEM) analysis, respectively. The synthesized hydrogels have been utilized for the elimination of Cu2+ and Co2+ ions from wastewater. The properties of prepared AMCLHs hydrogels, i.e. swelling and water retention ratio have been studied in distilled water under optimized conditions. The maximum swelling ratio of the best grade of hydrogel (AMCLHs-1) has been found to be 400.5 g/g with the water retention ratio of 75.09% during 24 h. These findings indicate the AMCLHs-1 hydrogel has remarkable swelling and water retention capacity. The maximum metal ion removal efficiency of AMCLHs-1 hydrogel from aqueous solutions has been found to be 96.6% for Cu2+ and 94.2% for Co2+ ions under optimum conditions. The experimental data fitted well with the Langmuir and Freundlich adsorption models, revealing maximum adsorption capacities of 431.03 mg/g for Cu2+ ions and 414.93 mg/g for Co2+ ions, respectively. In addition, the rate for the adsorption of Cu2+ and Co2+ ions onto AMCLHs-1 hydrogel follows both Pseudo first and second-order kinetic models. The negative ΔG values indicate that the adsorption process occurs spontaneously, while positive ΔH values suggest that the adsorption process is exothermic in nature. The prepared AMCLHs hydrogel is reusable and exhibits high desorption efficiency with 87.63% for Cu2+ and 85.21% for Co2+ metal ions even after the fourth cycle. Overall, AMCLHs hydrogel is a cost-effective and reusable adsorbent that possesses a significant potential for heavy metal ion removal from aqueous solutions.

Highly Asymmetric Lamellar Structure in Blends of Polystyrene-b-Poly(acrylic acid) Block Copolymers and Poly(4-vinylpyridine) Homopolymers Facilitated by Polyelectrolyte Complexation

Highly Asymmetric Lamellar Structure in Blends of Polystyrene-<i>b</i>-Poly(acrylic acid) Block Copolymers and Poly(4-vinylpyridine) Homopolymers Facilitated by Polyelectrolyte Complexation

Bidirectional Temperature‐Responsive Thermochromic Hydrogels With Adjustable Light Transmission Interval for Smart Windows

AbstractThermochromic smart windows have been widely developed for solar regulation to save building energy. However, most current smart windows still exhibit a single responsiveness to a specific temperature, which is not conducive to daytime energy saving or nighttime privacy protection. Herein, a low‐temperature response is achieved by pre‐initiation of the monomer acrylamide (AAm) and acrylic acid (AA) in the synthesis of P(AAm‐co‐AA). Then, N‐isopropyl acrylamide and AAm are introduced into P(AAm‐co‐AA) to form a pre‐polymerized precursor solution. The liquid precursor solution can be encapsulated within two quartz glasses and synthesized in situ to prepare smart windows, which exhibit a high visible light transmittance of 84.4%, excellent solar modulation of 69.5%, and bidirectional temperature responsiveness (cold and hot). In addition, the upper critical solution temperature and the lower critical solution temperature of the hydrogel and the light transmission interval between the two temperatures can be flexibly adjusted to adapt to different climates and individual user needs. The designed smart window maintains a high light transmission within the human body's comfort temperature range. The bidirectional temperature response window achieves the dual functions of energy saving and privacy protection, making it an ideal smart window candidate with good prospects for practical applications.

Methallylsulfonate Polymeric Antiscalants for Application in Thermal Desalination Processes.

Nine copolymers of acrylic acid and sodium methallyl sulfonate were tested as scale inhibitors in thermal desalination. The nine antiscalants covered molar masses between 2000 and 9500 g.mol-1 and concentrations of sulfonated monomer ranging between 10 and 30 mole percent. A pressure measurement and control (P-MAC) unit and a high-temperature pressurized vessel were used to measure the effectiveness of the scale inhibitors in seawater, concentrated seawater, and model solutions at 125 °C. The effectiveness of the novel copolymers was comparable to commercial antiscalant at times up to 15 min and improved at longer times. Molar mass was a more important determinant of effectiveness than degree of sulfonation, with the greatest mitigation of calcium sulfate precipitation observed for antiscalants of molar mass 2000 to 2500 g.mol-1 regardless of sulfonate content. Antiscalants of molar mass 4500 to 5000 g.mol-1 showed a higher threshold effect than antiscalants of molar mass 7000 to 9500 g.mol-1, with a 30% sulfonated polymer of molar mass 4500 g.mol-1 performing appreciably better than other polymers of a similar molar mass.

An Optical Au3+ Sensor Based on layer-by-layer PEI/PAA-Rho thin Films on ITO.

This study presents the development of a sensitive and selective gold ion (Au3+) sensor utilizing layer-by-layer (LbL) assembled thin films composed of polyethylenimine (PEI) and poly (acrylic acid) (PAA) conjugated with rhodamine (Rho). The first study revealed that the polymeric sensors (PAA-Rho) demonstrated significant selectivity and sensitivity in their colorimetric and fluorescence responses to Au3+ compared to other metal ions. In their spirolactam form, the polymeric sensors were non-fluorescent but could selectively transform into the fluorescent ring-opened amide form upon interaction with Au3+ ions, resulting in fluorescence enhancement and observable color changes. Common co-existing metal ions showed negligible interference in the detection of Au3+. The LbL sensor exhibited a linear increase in absorbance with the addition of bilayers, confirming successful film deposition. Surface morphology analysis using SEM, along with structural confirmation via ATR-FTIR and XRD, further validated the sensor's capability to detect cation. Results demonstrated that the LbL sensor exhibited selectivity for Au3+ ions within the range 1 × 10-6 to 1 × 10-3 M. This approach offers an easily understandable and intrinsically sensitive means for detecting Au3+ ions in both environmental and biological applications.

In Situ Formation of Acidic Comonomer during Thermal Treatment of Copolymers of Acrylonitrile and Its Influence on the Cyclization Reaction.

Binary and ternary copolymers of acrylonitrile (AN), tert-butyl acrylate (TBA), and n-butyl acrylate (BA) are synthesized through conventional radical polymerization in DMSO in the presence of 2-mercaptoethanol. The thermal behavior of binary and ternary copolymers is studied under argon atmosphere and in air. It is demonstrated that the copolymers of AN contain 1-10 mol.% of TBA split isobutylene upon heating above 160 °C, resulting in the formation of the units of acrylic acid in the chain. The carboxylic groups formed in situ are responsible for the ionic mechanism of cyclization, which starts at lower temperatures compared with pure polyacrylonitrile (PAN) or AN copolymer with BA. The activation energy of cyclization through ionic and radical mechanisms depends on copolymer composition. For the ionic mechanism, the activation energy lies in the range ca. 100-130 kJ/mole, while for the radical mechanism, it lies in the range ca. 150-190 kJ/mole. The increase in the TBA molar part in the copolymer is followed by faster consumption of nitrile groups and the evolution of a ladder structure in both binary and ternary copolymers. Thus, the incorporation of a certain amount of TBA in PAN or its copolymer with BA allows tuning the temperature range of cyclization. This feature seems attractive for applications in the production of melt-spun PAN by choosing the appropriate copolymer composition and heating mode.

Synthesis, Biological Evaluation and Reversal of Sulfonated Di- and Triblock Copolymers as Novel Parenteral Anticoagulants.

Despite targeting different coagulation cascade sites, all Food and Drug Administration-approved anticoagulants present an elevated risk of bleeding, including potentially life-threatening intracranial hemorrhage. Existing studies have not thoroughly investigated the efficacy and safety of sulfonate polymers in animal models and fully elucidate the precise mechanisms by which these polymers act. The activity and safety of sulfonated di- and triblock copolymers containing poly(sodium styrenesulfonate) (PSSS), poly(sodium 2-acrylamido-2-methylpropanesulfonate) (PAMPS), poly(ethylene glycol) (PEG), poly(sodium methacrylate) (PMAAS), poly(acrylic acid) (PAA), and poly(sodium 11-acrylamidoundecanoate) (PAaU) blocks are synthesized and assessed. PSSS-based copolymers exhibit greater anticoagulant activity than PAMPS-based ones. Their activity is mainly affected by the total concentration of sulfonate groups and molecular weight. PEG-containing copolymers demonstrate a better safety profile than PAA-containing ones. The selected copolymer PEG47-PSSS32 exhibits potent anticoagulant activity in rodents after subcutaneous and intravenous administration. Heparin Binding Copolymer (HBC) completely reverses the anticoagulant activity of polymer in rat and human plasma. No interaction with platelets is observed. Selected copolymer targets mainly factor XII and fibrinogen, and to a lesser extent factors X, IX, VIII, and II, suggesting potential application in blood-contacting biomaterials for anticoagulation purposes. Further studies are needed to explore its therapeutic applications fully.

Synthesis and properties of superhydrophobic monomer stearyl methacrylate-modified polyacrylate latex pressure sensitive adhesives

Hybrid surfactants of long carbon chain hydrophobic nonionic emulsifier N-390 and conventional anionic emulsifier CO-436 were utilized in this study to enable successful emulsion polymerization of super-hydrophobic monomer stearyl methacrylate (SMA) together with butyl acrylate (BA), acrylic acid (AA), and 2-hydroxyethyl acrylate (HEA). The influences of SMA on the resulting latex and film properties were thoroughly investigated. Both FTIR and 1H NMR were used to confirm the successful participation of SMA in the emulsion polymerization. The results indicated that with introduction of SMA, the roughness of the latex film increases, while the light transmission decreases. It was also found that with the addition of SMA, contact angle of the latex PSA film increased from 115.1° to 127.2°, while water absorption decreased from 5.76 to 2.89 wt%. DSC curves demonstrated that SMA has participated more in the homopolymerization reaction than in the copolymerization reaction. TGA results showed that the initial decomposition temperature (T5%) of the latex film was increased from 302.8 to 332.7 °C with the increase of SMA dosage from 0 to 20 wt%. Finally, adhesion properties results indicated that loop tack and 180° peel force of the PSA films were decreased from 11.51 to 1.88 N/25 mm and 6.36 to 3.44 N/25 mm, respectively, while shear strength was increased from 732 to 2865 min.