Article
Polymer Science
Na Liu, Doudou Liu, Bo Liu, Hao Zhang, Dongmei Cui
Summary: The reaction of heteroscorpionated ligands with homoleptic calcium amide resulted in the formation of new zwitterionic calcium complexes. These complexes were characterized and tested for their controlled polymerization of rac-lactide, showing linear increase in molecular weights with monomer-to-catalyst ratio. Surprisingly, at different temperatures, the complexes produced polylactides with different stereochemistries.
Article
Chemistry, Multidisciplinary
Jiang Dai, Wei Xiong, Dong-Yu Li, Zhongzheng Cai, Jian-Bo Zhu
Summary: By combining two stereogenic elements, we have successfully designed a series of bifunctional thiourea-based organocatalysts, which enable stereoselective polymerization of lactide to produce iso-enriched polylactide.
CHEMICAL COMMUNICATIONS
(2023)
Article
Polymer Science
Yi Wan, Yun Bai, Hai Xu, Jianghua He, Yuetao Zhang
Summary: The study successfully synthesized five chiral binuclear aluminum methyl complexes, which catalyze the ring-opening polymerization of rac-lactide in a controlled manner and produce polymers with high isoselectivity. The kinetic studies show a first-order dependence on monomer concentration, supporting an enantiomorphic site control mechanism for the catalysts. This strategy can also be applied to other lactones for ring-opening polymerization.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Julie Meimoun, Choltirosn Sutapin, Gregory Stoclet, Audrey Favrelle, Pascal Roussel, Marc Bria, Suwabun Chirachanchai, Fanny Bonnet, Philippe Zinck
Summary: The chain shuttling ring-opening copolymerization of L-lactide with epsilon-caprolactone using two aluminum catalysts and benzyl alcohol as a chain transfer agent has been successfully achieved. A newly synthesized aminobisphenolate supported aluminum complex affords lactone rich poly(L-lactide-co-lactone) statistical copolymeric blocks, while Al(OiPr)(3) produces semicrystalline poly(L-lactide) rich blocks. The crystalline ratios and glass transition temperatures of these new classes of polylactide based block copolymers can be tuned by adjusting the catalysts and the comonomers ratio.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Polymer Science
Zengping Peng, Hassan Ahmed, Guangqiang Xu, Xuanhua Guo, Rulin Yang, Hongguang Sun, Qinggang Wang
Summary: A series of unreported aluminium complexes with chiral cyclohexylsalen ligands were synthesized and used for the asymmetric kinetic resolution polymerization (AKRP) of rac-lactide (LA). These chiral complexes exhibited an interesting stereoselectivity-switch behavior in rac-LA polymerization. Among them, (R,R)-Salen[6-Cl] showed the highest activity for the ROP of rac-LA, while (R,R)-salen[4,6-Br,Bu-t] demonstrated excellent stereoselectivity with enriched isotactic PLA (P-m = 0.88, CEC; P-m = 0.93, ESC). Kinetic study using (R,R)-salen[4,6-Br,Bu-t] as an initiator indicated first-order dependence on monomer concentration with a rate constant ratio k(L)/k(D) = 30. Asymmetric kinetic resolution polymerization provided evidence that the enantiomorphic site control mechanism plays a major role in rac-LA ROP mediated by aluminium catalysts with a bulkier electron donor near the metal center, while the ROP of rac-LA mediated by Al(salen) catalysts with electron-withdrawing groups primarily occurs via the chain end control mechanism.
Article
Chemistry, Physical
Jonathan E. Chellali, Alexander K. Alverson, Jerome R. Robinson
Summary: This study reports a new class of Zn catalysts that exhibit high activity and stability in the ring-opening polymerization of lactide. Mechanistic studies revealed a quantitative structure-function relationship between the steric profile of the catalyst's reaction site and its activity, providing important insights for the design of homogeneous catalysts.
Article
Polymer Science
Zhedong Li, Shiwei Duan, Na Zhao, Zhibo Li
Summary: In this study, two bulky phenyl diphosphazene bases, p-PDPB and m-PDPB, were synthesized and used in combination with ureas and squaramides as hydrogen-bond donors to mediate stereocontrolled ring opening polymerization (ROP) of lactide. The phenyl diphosphazene based/urea binary catalytic system successfully synthesized semicrystalline PLAs with narrow dispersity and high tacticity (P-m up to 0.84) in a well-controlled manner. Structural analysis confirmed the linear structure and high end-group fidelity of the resulting polymers, and MALDI-TOF MS analysis indicated the good controllability of the binary catalytic system with minimal transesterification.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Inorganic & Nuclear
Liu Zhu, Ya Xu, Dan Yuan, Yaorong Wang, Yingming Yao
Summary: A series of lanthanide monoborohydride complexes stabilized by bulky beta-diketiminato ligands were synthesized and examined for their catalytic behaviors in the ring-opening polymerization of lactide. The complexes were found to efficiently initiate the ring-opening polymerization of L-lactide and rac-lactide to produce alpha,omega-telechelic polylactide diols. The solid-state structures of these lanthanide complexes were determined by single-crystal X-ray diffraction.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Folkert de Vries, Edwin Otten
Summary: This article describes the redox-switching of a formazanate zinc catalyst in ring-opening polymerization of lactide. The catalytic activity can be modulated by reversible reduction/oxidation chemistry at a purely organic fragment, achieved by using a redox-active ligand bound to an inert metal ion (Zn2+). Kinetic and spectroscopic studies, along with mass spectrometry analysis of the catalysis mixture, provide insights into the nature of the active species and the initiation of lactide ring-opening polymerization. The mechanistic data highlights the crucial role of the redox-active ligand and offers an explanation for the formation of cyclic polymer.
Article
Polymer Science
Alexander Balint, Stefan Naumann
Summary: By utilizing catalyst pairs of N-heterocyclic olefins (NHOs) and metal-based Lewis acids for lactide polymerization, precise control over polymerization mechanism and NHO placement with quantitative selectivity is achievable. The co-catalytic approach proves superior to metal-free polymerization, providing access to well-defined PLA or high reaction rates. The dominance of metal halide in determining general polymerization performance and stereoselectivity is emphasized, showcasing the potential for preparing specific PLA structures through manipulation of catalyst setup.
Article
Polymer Science
Lidong Feng, Xinchao Bian, Gao Li, Xuesi Chen
Summary: The study shows that the compatibility between PLLA and PLDLA-m decreases as the L-lactate unit content in PLDLA-m decreases, impacting the crystallization and compatibility of the blends.
Article
Chemistry, Multidisciplinary
Jayeeta Bhattacharjee, Alok Sarkar, Tarun K. Panda
Summary: This review highlights the progress of alkali metal-based catalysis for the ring opening polymerization of rac-lactide, critically assesses futuristic research, spotlights major developments achieved in the past few years, and provides an overview of the challenges and opportunities.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Shweta Sagar, Kulsum Bano, Alok Sarkar, Kuntal Pal, Tarun K. Panda
Summary: A novel sulfur-supported magnesium complex was developed as a catalyst for ring-opening polymerization of rac-lactide and epsilon-caprolactone. This catalyst showed high selectivity for rac-lactide polymerization, resulting in isoselective PLA with a P-i value of 0.77. The polymerization proceeded under mild reaction conditions without the need for an external initiator, and the resulting polyesters exhibited good control over the molecular weight.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Polymer Science
Cristina Ruiz Martinez, Juana M. M. Perez, Francisco M. M. Arrabal-Campos, Antonio Rodriguez-Dieguez, Duane Choquesillo-Lazarte, Juan A. A. Martinez-Lao, Manuel A. A. Ortuno, Ignacio Fernandez
Summary: We report the synthesis and characterization of three novel lithium complexes (2b-d) with different hydrazonyl anthraquinonic backbones, tested in the ring-opening polymerization (ROP) of lactide and epsilon-caprolactone for synthesizing cyclic polymers. Various analytical methods, including NMR, MS spectrometry, and FTIR spectroscopy, are used to identify the catalyst structures. The resulting cyclic polymers are characterized using MALDI-TOF, end-group NMR analysis, and PGSE diffusion NMR. Differences in selectivity (linear vs cyclic) are observed when using ligand backbones with different abilities and/or steric restrictions.
Article
Polymer Science
Fangping Ren, Xinlei Li, Ji Xian, Xinning Han, Luya Cao, Xiaobo Pan, Jincai Wu
Summary: This study reports three bench-stable potassium phenolates as isoselective catalysts for the ring-opening polymerization of lactides. These catalysts exhibit high activity under moisture conditions and allow for controllable polymerization reactions.
JOURNAL OF POLYMER SCIENCE
(2022)
Article
Engineering, Environmental
Srabanti Ghosh, Georgiana Amariei, Marta E. G. Mosquera, Roberto Rosal
Summary: This study demonstrates the significant antibacterial activity of the polymeric precursor [Ru(CO)(2)Cl-2](n) at nanogram levels, particularly enhanced under photoirradiation, while remaining biocompatible.
JOURNAL OF HAZARDOUS MATERIALS
(2021)
Article
Chemistry, Inorganic & Nuclear
Irene Reviejo, Joan Vinueza, Javier Ramos, Marta E. G. Mosquera, Vanessa Tabernero, Gerardo Jimenez
Summary: The reaction resulted in novel constrained-geometry chiral titanium complexes and corresponding alkyl derivatives. The protonation reaction of the methyl complex was specific and reversible, leading to the formation of strain-free alkoxide- and thiolate-methyl compounds.
Article
Biochemistry & Molecular Biology
Tamara Rodriguez-Prieto, Sylwia Michlewska, Marcin Holota, Maksim Ionov, F. Javier de la Mata, Jesus Cano, Maria Bryszewska, Rafael Gomez
Summary: This study focused on synthesizing Ru metallodendrimers and imidazolium salt dendrimers, which showed promising anticancer activity at high generations and the ability to form dendriplexes with siRNA, suggesting a novel dual-action approach for cancer treatment.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2021)
Article
Chemistry, Organic
David Sanchez-Roa, Marta E. G. Mosquera, Juan Campora
Summary: Zwitterionic adducts of N-heterocyclic carbene and carbodiimide (NHC-CDI) are utilized as catalyst precursors for the valorization of dichloromethane into high added value products in a mild and efficient process. The resulting derivatives are isolated in quantitative yields, showcasing the potential for recycling dichloromethane excess. Mechanistic studies suggest a phase-transfer catalysis mechanism for the synthesis of methylal CH2 (OMe)(2).
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Polymer Science
Andres Cardil, Miguel Palenzuela, Juan F. Vega, Marta E. G. Mosquera
Summary: A recent study has successfully produced nano-sized macromolecular assemblies through a combined polymerization process of glycidyl methacrylate mediated by aluminum complexes. The morphological features and rheological properties of these novel nanoassemblies were investigated. The study revealed that the nanoparticles exhibited a thin disk shape on a flat surface, and their rheological behavior resembled that of un-entangled polymers.
Article
Polymer Science
Christian Rentero, Jesus Damian, Asier Medel, Maria Fernandez-Millan, Yolanda Rusconi, Giovanni Talarico, Tomas Cuenca, Valentina Sessini, Marta E. G. Mosquera
Summary: By studying the activity and mechanism of two non-toxic potassium compounds as catalysts for the ROP process of LLA, it was found that they can polymerize the monomer quickly, and the molecular structure and solubility of the compounds have certain effects on the polymerization process.
Article
Chemistry, Inorganic & Nuclear
Vanessa Tabernero, M. Teresa Munoz, Miguel Palenzuela, Rosa M. Gomila, Antonio Frontera, Marta E. G. Mosquera
Summary: This communication presents the synthesis and X-ray characterization of a novel mononuclear aluminium compound with an intramolecular sigma-hole triel bonding interaction. It is compared with a previously reported dinuclear aluminium compound, where the aluminium atoms participate in two concurrent sigma-hole triel bonding interactions. This behavior has not been described in the literature before.
DALTON TRANSACTIONS
(2023)
Review
Nanoscience & Nanotechnology
Francisco Javier de la Mata, Rafael Gomez, Jesus Cano, Javier Sanchez-Nieves, Paula Ortega, Sandra Garcia Gallego
Summary: This article summarizes the recent advances in the pharmaceutical applications of carbosilane dendritic molecules, showcasing their potential in various areas from therapeutics to diagnostics and prevention tools.
WILEY INTERDISCIPLINARY REVIEWS-NANOMEDICINE AND NANOBIOTECHNOLOGY
(2022)
Article
Chemistry, Inorganic & Nuclear
Diego Jaraba Cabrera, Ryan D. Lewis, Carlos Diez-Poza, Lucia Alvarez-Miguel, Marta E. G. Mosquera, Alex Hamilton, Christopher J. Whiteoak
Summary: This study investigates the synthesis of aluminum, gallium, and indium compounds supported by a readily prepared salphen ligand and explores their structures and potential as catalysts for the synthesis of cyclic carbonates. It is demonstrated that the indium compounds are the most active catalysts, despite their lower Lewis acidity compared to aluminum compounds. A Density Functional Theory (DFT) study provides important insights into the reasons for the high activity of the indium catalyst.
DALTON TRANSACTIONS
(2023)
Article
Polymer Science
Miguel Palenzuela, Juan F. Vega, Virginia Souza-Egipsy, Javier Ramos, Christian Rentero, Valentina Sessini, Marta E. G. Mosquera
Summary: In this study, the polymerization of limonene oxide (LO) was optimized using two different aluminium-based catalysts (AlMeX{2,6-(CHPh2)(2)-4-Bu-t-C6H2O}, where X = Me (1), Cl (2)) at room temperature. A bio-based ether, polylimonene oxide (PLO), with low molecular weight and good thermal stability, was successfully synthesized and could be used as a sustainable polymeric additive for bio-based and biodegradable polymers such as polylactic acid (PLA). Blends of PLA and PLO were prepared through melt processing to investigate the influence of PLO on the thermal, mechanical, and morphological properties of PLA. The addition of a small amount of PLO led to a significant decrease in the glass transition temperature of PLA, as well as a decrease in melting temperature and degree of crystallinity, while increasing the flexibility of PLA-based films. These results indicate strong interactions between the components, suggesting partial miscibility.
Review
Chemistry, Organic
Carlos Diez-Poza, Lucia Alvarez-Miguel, Marta E. G. Mosquera, Christopher J. J. Whiteoak
Summary: Cyclic thiocarbonates, sulfur analogues of cyclic carbonates, have been relatively underexplored despite their potential applications and intriguing reactivities. They have been used as monomers for polythiocarbonate synthesis and reactive intermediates for the preparation of sulfur containing compounds. However, the synthesis of these compounds lags behind their non-sulfur analogues. This article provides an overview of the state-of-the-art synthesis and applications of cyclic mono-, di-, and tri-thiocarbonates.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Lucia Alvarez-Miguel, Marta E. G. Mosquera, Christopher J. Whiteoak
Summary: The study demonstrates the conversion of erucic acid from rapeseed oil into value-added compounds and presents new methods for synthesizing different cyclic compounds. These compounds have potential applications in the synthesis of bio-based polyurethane.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Materials Science, Biomaterials
Srabanti Ghosh, Georgiana Amariei, Marta E. G. Mosquera, Roberto Rosal
Summary: This study demonstrates the strong antimicrobial activity of conjugated polymer nanostructures (CPNs) as photoactivated compounds against Gram-positive and Gram-negative microorganisms. The effect is attributed to the photoinduced generation of reactive oxygen species, leading to cell membrane damage and inhibition of biofilm formation. The CPNs show potential advantages for biomedical applications due to their broad antibacterial spectrum, biofilm inhibition, and lack of acute toxicity.
JOURNAL OF MATERIALS CHEMISTRY B
(2021)
Article
Chemistry, Analytical
Karolina Kowalewska, Tamara Rodriguez-Prieto, Slawomira Skrzypek, Jesus Cano, Rafael Gomez Ramirez, Lukasz Poltorak
Summary: This study focused on the electroanalytical study of a family of five imidazolium-terminated carbosilane dendrimers at the polarized liquid-liquid interface. The dendrimers were found to be electrochemically active and undergo interfacial ion transfer processes, contributing to the understanding of the interaction between branched macromolecules and biomimetic interfaces.