Synthesis, antimicrobial activity and application of polymers of praseodymium complexes based on pyridine nitrogen oxide.

The traditional pyridine nitrogen oxide-based antimicrobial agents are often associated with health risks due to heavy metal enrichment. To mitigate this concern, we synthesized two novel complexes, Pr2(mpo)6(H2O)2 and Pr(hpo)(mpo)2(H2O)2, and integrated rare-earth salts, Hhpo (2-hydroxypyridine-N-oxide) and Nampo (2-mercapto-pyridine-N-oxide sodium salt). These complexes were characterized through infrared analysis, elemental analysis, thermogravimetric analysis, and X-ray crystallographic analysis. Our comparative analyses demonstrate that the synthesized rare-earth complexes exhibit stronger antimicrobial activity against Staphylococcus aureus (S. aureus ATCC6538) and Escherichia coli (E. coli ATCC25922) compared to the ligands and rare-earth salts alone. Quantitative results revealed the lowest inhibitory concentrations of the two complexes against S. aureus ATCC6538 and E. coli ATCC25922 at 3.125 µg mL-1, 6.25 µg mL-1, 3.125 µg mL-1 and 6.25 µg mL-1, respectively. Preliminary investigations indicated that the antibacterial mechanism of these complexes involved promoting intracellular substance exudation to achieve antibacterial effects. Incorporation of these complexes into polymeric antimicrobial films resulted in a potent antimicrobial effect, achieving a 100% inhibition rate against S. aureus ATCC6538 and E. coli ATCC25922 at a low addition level of 0.6 wt%. Our results suggest that nitrogen oxide-based praseodymium complexes have potential for various antimicrobial applications.

Synthesis of cerium-based flame retardant containing phosphorus and its impact on the flammability of polylactic acid.

The synthesis and characterization of [Ce2(PPPA)4(OH)2]·4H2O, wherein PPPA denotes 3-(hydroxy(phenyl)phosphoryl)propanoate, were conducted. Its potential as a flame-retardant additive for poly(L-lactic acid) (PLA) in conjunction with ammonium polyphosphate (APP) was investigated. Remarkably, with just incorporation of the 1 % Ce-complex and 4 % APP, the resulting PLA composite (PLA-8) meets the V-0 standard, exhibiting an impressive limiting oxygen index (LOI) of 29.4 %. Moreover, the introduction of the Ce-complex leads to a significant extension of ignition time (TTI), a significant 24.1 % decrease in total heat release (THR) compared to pure PLA, and a notable increase in residual carbon rate from 0.3 % to 3.51 %. Although PLA-8 exhibits a minor decline of 8.7 % in tensile strength and 3.4 % in elongation at break, respectively, compared to pure PLA, there is a substantial improvement of 32.2 % in Young's modulus and 29.9 % in impact resistance. These results emphasise the potential of cerium-based phosphorus-containing flame retardants, with cerium playing a key role in enhancing the flammability characteristics of PLA. This study contributes to the development of sustainable and fire-resistant materials in polymer chemistry.

UV-barrier poly(lactic acid) film with light-stabilized Eu complexes as filler.

The poor UV shielding property of PLA limit it further applications on food packaging. The rare-earth complex Eu(DBM)3phen converts absorbed ultraviolet (UV) light to red light, which inspires the development of new UV shielding materials. However, this complex has low photostability and decomposes easily under UV irradiation. Thus, we prepared a long-lasting rare-earth complex transluminant Eu(DBM)2(BP-2)phen by introducing BP-2 into Eu(DBM)3phen, and blended it with PLA to obtain PLA/Eu(DBM)2(BP-2)phen composite films. The test results showed that the complex could reduce the UV transmittance of PLA films by emitting luminescence and heat. The UV transmittance of the composite film with 0.5 % mass fraction decreased from 87.4 % to 7.7 %, compared to pure PLA films, and remained at 11.6 % after 12 days of UV aging. The film had long-lasting UV shielding performance, good transparency and mechanical properties. Finally, In the storage experiments of flaxseed oil, the P/E25 film effectively retarded the oxidation process of the oil.

Synthesis, Characterization, and Applications of Rare-Earth-Based Complexes with Antibacterial and Antialgal Properties.

The pursuit of environmentally friendly and highly effective antifouling materials for marine applications is of paramount importance. In this study, we successfully synthesized novel rare earth-based complexes by coordinating cerium (Ce III), samarium (Sm III), and europium (Eu III) with pyrithione (1-hydroxy-2-pyridinethione; PT). Extensive characterizations were performed, including single-crystal X-ray analysis, which revealed the intriguing binuclear structure of these complexes. This structural motif comprises two rare-earth ions intricately double-bridged by two oxygen atoms from the PT ligand, resulting in a distinctive and intriguing geometry. Furthermore, the central rare earth ion is surrounded by three sulfur atoms and two additional oxygen atoms, forming a unique distorted bicapped trigonal prismatic configuration. Compared with conventional antifouling biocides such as sodium pyrithione (NaPT), copper pyrithione (CuPT), and zinc pyrithione (ZnPT), these newly synthesized rare-earth complexes exhibited a remarkable boost in their in vitro antibacterial efficacy against both Gram-positive and Gram-negative bacteria. Additionally, these complexes demonstrated significant potential as antialgal agents, displaying impressive activity against marine planktonic organisms. These findings underscore the promising application prospects of these rare-earth complexes in the field of marine antifouling.

Green and economic flame retardant prepared by the one-step method for polylactic acid.

Resolving the flammability of poly(L-lactic acid) (PLA) while ensuring its environmental friendliness and preserving key flame retardancy and mechanical properties represents a critical challenge. We have successfully developed a highly efficient and environmentally friendly flame retardant called Hexamethylenediamine tetramethylene phosphonic acid amine (HDME). The flame retardancy of PLA/HDME composites was significantly improved, as indicated by the LOI value of 29.1 % and UL-94 V-0 rating for PLA/3.5 HDME with only 3.5 % HDME addition. The results show a 23.4 % reduction in the total heat release (THR), a 40.0 % increase in the time to ignition (TTI), and a 21.2 % increase in the flame propagation index (FPI) compared to original PLA. Flame retardant mechanism of HDME involves the gas phase, condensed phase, and interrupted heat exchange effects. The HDME also preserved the original mechanical properties of PLA, with the elongation at break and tensile strength retention of PLA/3.5 HDME reaching 93.05 % and 89.65 %. This work provides a simple and efficient method for flame retardant modification of PLA, which can expand its application scope.

Mixed exposure effect of seminal metals on semen quality, mediation of total antioxidant capacity, and moderation of GSTM1/GSTT1 gene deletion in Chinese reproductive-aged men.

BACKGROUND: The effects of metal exposure on semen quality and the role of oxidative damage in this process remain unclear. METHODS: We recruited 825 Chinese male volunteers, and 12 seminal metals (Mn, Cu, Zn, Se, Ni, Cd, Pb, Co, Ag, Ba, Tl, and Fe), the total antioxidant capacity (TAC), and reduced glutathione were measured. Semen parameters and GSTM1/GSTT1-null genotypes were also detected. Bayesian kernel machine regression (BKMR) was applied to evaluate the effect of the mixed exposure to metals on semen parameters. The mediation of TAC and moderation of GSTM1/GSTT1 deletion were analyzed. RESULTS: Most seminal metal concentrations were correlated with each other. The BKMR models revealed a negative association between the semen volume and metal mixture, with Cd (cPIP = 0.60) and Mn (cPIP = 0.10) as the major contributors. Compared to fixing all scaled metals at their median value (50th percentiles), fixing the scaled metals at their 75th percentiles decreased the TAC by 2.17 units (95%CI: -2.60, -1.75). Mediation analysis indicated that Mn decreased the semen volume, with 27.82% of this association mediated by TAC. Both the BKMR and multi-linear models showed that seminal Ni was negatively correlated with sperm concentration, total sperm count, and progressive motility, which was modified by GSTM1/GSTT1. Furthermore, Ni and the total sperm count showed a negative association in GSTT1 and GSTM1 null males (ß[95%CI]: 0.328 [-0.521, -0.136]) but not in males with GSTT1 and/or GSTM1. Although Fe and the sperm concentration and total sperm count were positively correlated, they showed inverse "U" shapes in univariate analysis. CONCLUSION: Exposure to the 12 metals was negatively associated with semen volume, with Cd and Mn as the major contributors. TAC may mediate this process. GSTT1 and GSTM1 can modify the reduction in the total sperm count caused by seminal Ni exposure.

Developing a cerium lactate antibacterial nucleating agent for multifunctional polylactic acid packaging film.

With the rapid development of the packaging industry, people have high requirements for the functionality of packaging materials. As a representative biodegradable packaging material, polylactic acid (PLA) still has some problems. Multifunctional additives in PLA are an effective modification method. In this paper, cerium lactate (Ce-LA) was synthesized by a precipitation method and integrated into PLA to prepare a functional PLA composite. The results showed that Ce-LA not only significantly improved the crystallinity but also imparted antibacterial ability to PLA. When the concentration of Ce-LA was 0.9 %, the crystallinity of PLA reached 39.35 %, which was 77 % higher than that of pure PLA. When the addition of Ce-LA was 1.8 %, the antibacterial rates of PLA against Staphylococcus aureus and Escherichia coli reached 93 % and 85 %, respectively. This study provides a beneficial solution for the development of PLA packaging materials with high crystallinity and antibacterial properties.

Polylactic Acid/Cerium Fluoride Films: Effects of Cerium Fluoride on Mechanical Properties, Crystallinity, Thermal Behavior, and Transparency.

PLA is widely used in the field of disposable products for its good transparency, high strength, high modulus, and good processing performance. However, the crystallization rate and crystallinity of PLA are weak. In actual production, the PLA products that are typically obtained are amorphous with poor heat resistance, which greatly limits the application range of PLA products. Finding an effective nucleating agent to improve the transparency of PLA has been a hot topic in research. This study found that Cerium fluoride (CeF3) can effectively improve the crystallinity of PLA/CeF3 (P/F) films. When the content of CeF3 in PLA was 1 wt %, the retention ratio of visible light transmittance was 82.36%, the crystallinity was 29.8%, and the tensile strength was 59.92 MPa. Compared to pure PLA, the crystallinity of P/F1 increased by 56% and tensile strength increased by 8.76%. This study provided an alternative scheme that maintained the PLA film's transparency and improved the crystallinity of PLA, which significantly expanded the application of PLA.