Article
Engineering, Chemical
Xue Huang, Yunqi Wang, Qingguo Wang, Jing Zhang
Summary: This work successfully synthesized a catalyst with high surface area and Cu(0) particles encapsulated in a hierarchically mesoporous structure. The catalyst exhibited high efficiency for adsorption and degradation of tetracycline hydrochloride, with wide pH adaptation and great recycled performance. The oxidative effectiveness was due to both radical and non-radical pathways.
SEPARATION AND PURIFICATION TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Hongxing Yuan, Xinhao Wan, Jianqi Ye, Tuotuo Ma, Fangyuan Ma, Jie Gao, Wei Gao, Dan Wen
Summary: Here, a general molecular engineering strategy was reported to synthesize molecule-noble metal aerogels (M-NMAs) via 3D assembly of metal nanoparticles induced by metalloporphyrin as cross-linkers. Due to the well synergy of NMAs and porphyrin molecule in creating the facile reaction pathway for ORR catalysis, these M-NMAs demonstrate boosted ORR activity and durability in different electrolytes. The PtPd-based M-NMA delivers superior ORR electrocatalytic performance compared to the commercial Pt/C catalyst.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Organic
Xiaosheng Luo, Ping Wang
Summary: In this study, the conversion of 4-aryl-1,4-dihydropyridines (DHPs) into ynones under electrochemical conditions is reported. The reaction proceeds via the homolysis of acyl-DHP under electron activation and resulting acyl radicals react with hypervalent iodine(III) reagents to form the target ynones or ynamides in acceptable yields. This methodology shows wider functionality tolerance and synthetic utility for late-stage modification of complex molecules.
Article
Chemistry, Multidisciplinary
Matthieu Balas, Asma Mayoufi, Richard Villanneau, Franck Launay
Summary: Since its first report in the early 1990s, Mukaiyama-type aerobic epoxidation involving the presence of an aldehyde as an electron donor is considered as an interesting oxidation reaction. Among the various metal catalysts efficient for this process, salen-type complexes have many advantages: i) cheap Schiff-base ligands can be easily synthesized and functionalized, ii) their metal complexes are described with most transition metals from the periodic table and iii) these compounds are also efficient for the catalytic formation of cyclic carbonates from epoxides and CO2, which makes them ideal candidates for the oxidative carboxylation of alkenes. The present work aimed at revisiting the aerobic oxidation of styrene using Cr(iii) and Mn(iii) salen complexes in the presence of isobutyraldehyde with the idea to further use these complexes (without any work-up), as co-catalysts for the formation of styrene carbonate under CO2 pressure. However, contrary to what is often described in the literature, the present study showed that the introduction of a metal catalyst is not necessary for the epoxidation of styrene at 80 degrees C in benzonitrile. In our hands, yields of ca. 15% of styrene carbonate were obtained from styrene using O-2 (3.5 bar) and CO2 (11 bar) as reagents in the presence of isobutyraldehyde (2.5 eq), tetrabutylammonium bromide (ca. 2 mol%) and the Cr(iii) salen complex (ca. 1 mol%). Apparently, the oxidation of Cr(iii) to Cr(vi) species in the presence of O-2 and isobutyraldehyde is detrimental to the kinetics of the tetrabutylammonium bromide-catalyzed cycloaddition of CO2 to styrene oxide.
REACTION CHEMISTRY & ENGINEERING
(2023)
Article
Nanoscience & Nanotechnology
Zi-Hao Long, Dong Luo, Kun Wu, Zi-Ye Chen, Ming-Min Wu, Xiao-Ping Zhou, Dan Li
Summary: A new type of metal-organic framework was studied as a photocatalyst for the degradation of chemical warfare agents, effectively oxidizing sulfur mustard simulant and proposing a new detoxification strategy.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Multidisciplinary Sciences
Shi-Chao Ren, Xing Yang, Bivas Mondal, Chengli Mou, Weiyi Tian, Zhichao Jin, Yonggui Robin Chi
Summary: This study reports a decarboxylative radical coupling of carboxylic acids and acyl imidazoles catalyzed by an N-heterocyclic carbene and photocatalyst. The carboxylic acids serve as direct radical precursors, and suitable acyl imidazoles can also be generated in situby a reaction with CDI. The method is extended to three-component coupling by using alkenes as a third coupling partner via a radical relay process. The mild reaction conditions, simplicity, and use of easily available starting materials make this method a powerful strategy for constructing complex ketones and modifying natural products and medicines.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Ting-wei Wang, Zhen-xin Yi, Lu Zhang, Yi-kai Wang, Yan Li, Jian-guo Zhang
Summary: Guided by structural chemistry and crystallization chemistry, two coordination polymers Cu(AOCA)2(NO3)2 (ECPs-1) and [Cu(PZCA)(NO3)](NO3) (ECPs-2) were prepared and characterized. The study found that both ECPs-1 and ECPs-2 have the potential to be used as pyrotechnics, with ECPs-1 having a higher purity of 79%.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Engineering, Environmental
Ruoyu Sun, Juntong Liu, Yinsu Wu, Shengtao Xing
Summary: By introducing Zr into MnOX, the oxygen mobility was enhanced, leading to improved performance of PMS catalyst. The Zr-Mn composite oxides exhibited high selectivity and efficiency for the degradation of organic pollutants through a non-radical mechanism. ZM2 sample with a Zr:Mn ratio of 1:1 showed the highest activity, indicating the potential application of this catalyst in wastewater treatment.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Dirk Auman, Felix Ecker, Sophie L. Mader, Kevin M. Dorst, Alois Braeuer, Goran Widmalm, Michael Groll, Ville R. I. Kaila
Summary: In this study, we combine high-resolution X-ray crystallography, enzyme engineering, quantum-classical (QM/MM) simulations, and biochemical assays to uncover the existence of a peroxidic intermediate bridging the substrate and active site metal ion in AsqJ. We also find that the homolytic cleavage of this intermediate during substrate epoxidation generates an activated high-valent ferryl (FeIV = O) species for mediating the next catalytic cycle. These combined findings provide important insights into the chemical bond activation principles and molecular mechanisms of dioxygenases in complex enzymatic reaction networks.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Sandra Rabaca, Isabel C. Santos, Goncalo Lopes, Vasco da Gama, Luis F. Veiros, Manuel Almeida
Summary: The importance of C-H···N-C interactions in crystal engineering of conducting materials has been demonstrated by a new type of conducting material. The unique bilayer structure of the compound is due to the network of CH···N-C interactions.
Article
Chemistry, Organic
Kui Wang, Xiaoyu Liu, Siyu Yang, Yan Tian, Mingyang Zhou, Jianhua Zhou, Xiaofei Jia, Baoying Li, Siyuan Liu, Jianbin Chen
Summary: Molecular electrophotocatalysis is a powerful strategy for sustainable synthesis, and has been applied in a versatile electrophotocatalytic deaminative alkylation approach. The key point lies in the in situ recycling of alkyl radicals, and the method has also been successfully applied in ligand modification and late-stage functionalization of pharmaceuticals.
Article
Chemistry, Applied
Wonjin Jeon, Ji-Yeon Park, Min-Cheol Kim, Seung-Jae Lee, Deog-Keun Kim
Summary: Various transition metal-based Al2O3 catalysts show significantly different activities in the epoxidation of methyl oleate using H2O2 and O2 as oxidants. The reactivity in H2O2-based epoxidation is proportional to the acidity of the catalysts, while in O2-based epoxidation, it depends on the redox properties of the catalysts and O2 behavior on the catalyst surface. Mo and Cu-based catalysts exhibit outstanding performance with H2O2 and O2 via different reaction pathways. These findings provide valuable insights for designing catalytic reaction processes based on the type of oxidizing agent.
Article
Chemistry, Organic
Ramdas Sreedharan, Thirumanavelan Gandhi
Summary: alpha-Branched amines bearing beta-carbonyl in isoindolinones were synthesized via the aroylation of C(sp (3))-H carbon adjacent to the nitrogen atom. Unactivated tertiary amides and unactivated alkyl esters were used as electrophile sources. The reaction showed high functional group compatibility and could be applied to a range of substrates, including organometallic ferrocenyl esters and indole methyl esters with an acidic NH moiety.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Youngsuk Kim, Jung Eun Byeon, Gu Yoon Jeong, Seoung Su Kim, Hayoung Song, Eunsung Lee
Summary: This study presents the design and synthesis of a novel organic radical based on a 1,2-dicarbonyl scaffold supported by N-heterocyclic carbenes (NHCs), which exhibits remarkable stability due to the steric and electronic stabilization provided by the two NHC moieties. The radical cations can tolerate various harsh conditions and surpass the stability of triphenylmethyl and TEMPO radicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Dianwen Hu, Xiaojing Song, Hao Zhang, Xinyu Chang, Chen Zhao, Mingjun Jia
Summary: Catalytic epoxidation of styrene with molecular oxygen using transition metal monosubstituted heteropolyacid compounds encapsulated in UiO-66 frameworks shows high catalytic activity and selectivity, with Co-HPA@UiO-66 exhibiting the best performance under mild conditions. The hybrid composite catalyst efficiently converts styrene derivatives to epoxides through the activation of in-situ generated acylperoxy radical intermediate.
MOLECULAR CATALYSIS
(2021)
Article
Engineering, Chemical
A. S. Gaspar, J. B. Cordeiro, P. A. Simoes, D. Gameiro, F. A. Rocha, A. C. Serra, J. F. J. Coelho, A. C. Fonseca
Summary: Poly(beta-pinene) was used as a tackifier in hot melt adhesives for the first time, improving thermal stability and crystallization properties of the formulations while increasing material homogeneity. Higher amounts of poly(beta-pinene) resulted in stiffer materials and increased viscosity in the formulations.
INTERNATIONAL JOURNAL OF ADHESION AND ADHESIVES
(2022)
Article
Polymer Science
Vanessa A. Pereira, Patricia Mendonca, Jorge F. J. Coelho, Armenio C. Serra
Summary: A bio-based eutectic mixture was used as a solvent for the atom transfer radical polymerization (ATRP) of hydrophobic and hydrophilic monomers, resulting in well-defined homopolymers and amphiphilic block copolymers. This unique solvent system provides a convenient method for the synthesis of ABs.
Article
Chemistry, Applied
Talita C. Rezende, Joana C. M. Silvestre, Patricia Mendonca, Jorge Moniz, Armenio C. Serra, Jorge F. J. Coelho
Summary: In this work, a new type of polymeric dispersants were synthesized and used for the dispersion of titanium dioxide particles in water-based paint formulations. The dispersants showed high dispersion efficiency and improved gloss and pigment dispersion compared to a standard commercial dispersing agent. This study provides valuable insights into the development of efficient additives for water-based paints.
PROGRESS IN ORGANIC COATINGS
(2022)
Review
Nanoscience & Nanotechnology
Patricia Alexandra Pereira, Maria Elisa Silva Serra, Armenio C. Serra, Jorge F. J. Coelho
Summary: Nucleic acid-based therapies have revolutionized cancer treatment, but their short half-life and the need for multiple administrations have led to the development of innovative formulations using vinyl polymer-based materials. This review highlights the importance of vinyl polymers in protecting and delivering nucleic acids in cancer treatment.
WILEY INTERDISCIPLINARY REVIEWS-NANOMEDICINE AND NANOBIOTECHNOLOGY
(2022)
Article
Polymer Science
Carlos T. B. Paula, Ana B. Madeira, Patricia Pereira, Rita Branco, Paula V. Morais, Jorge F. J. Coelho, Ana C. Fonseca, Armenio C. Serra
Summary: This study developed an innovative degradable wound dressing by modifying poly(ethylene glycol) (PEG) to be responsive to reactive oxygen species (ROS), resulting in good mechanical properties and water uptake. The dressing also demonstrated the ability to load drugs and exhibit antibacterial activity.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Engineering, Biomedical
Rita G. Fonseca, Francesco De Bon, Patricia Pereira, Francisca M. Carvalho, Marta Freitas, Mahmoud Tavakoli, Armenio C. Serra, Ana C. Fonseca, Jorge F. J. Coelho
Summary: This study presents highly stretchable and tough hydrogels with controlled light-triggered photo-degradation for the first time. The hydrogels are formed by a double-network structure with covalently and ionically crosslinked subnetworks. By using a novel crosslinker, the mechanical properties of the hydrogel were not affected. The hydrogels show potential applications in health, electronics, and energy due to their excellent mechanical properties and controlled degradation.
MATERIALS TODAY BIO
(2022)
Article
Engineering, Environmental
Francesco De Bon, Rita G. Fonseca, Francesca Lorandi, Armenio C. Serra, Abdirisak A. Isse, Krzysztof Matyjaszewski, Jorge F. J. Coelho
Summary: This study reveals the scale-up of electrochemically mediated atom transfer radical polymerization (seATRP) from small to large scale. By optimizing reaction parameters and using renewable energy, self-degassing and efficient polymerizations were achieved, resulting in well-defined polymers with narrow molecular weight distributions. These findings could promote the widespread use of controlled radical polymerizations in the polymer industry.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Polymer Science
Rafael C. Rebelo, Luis P. C. Goncalves, Ana C. Fonseca, Josefa Fonseca, Manuel Rola, Jorge F. J. Coelho, Filipe Rola, Armenio C. Serra
Summary: This study investigated the degradation behavior of Bio-Flex (R), a blend of poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT), through simulated laboratory tests simulating outdoor accelerated weathering (OAW) and degradation in marine environments in seawater (MES). The results showed that acids were highly effective in degrading the PLA/PBAT blend, even during the blending process. The esters of DCA were found to be suitable additives for enhancing the degradation process of the PLA/PBAT blend.
Article
Materials Science, Paper & Wood
Rafael C. Rebelo, Diana C. M. Ribeiro, Patricia Pereira, Francesco De Bon, Jorge F. J. Coelho, Armenio C. Serra
Summary: A process combining two natural-based products was developed to obtain bio-based films. A cellulose/ESBO solution was prepared using a distillable and recyclable ionic liquid-based solvent. The resulting cellulose films exhibited flexible and solvent-free characteristics, with the presence of triglyceride structures and the absence of epoxide rings. The films showed adjustable flexibility and hydrophilicity properties due to the presence of ESBO, making them suitable for various applications.
Article
Engineering, Environmental
Francesco De Bon, Ana B. Barbosa, Rita G. Fonseca, Marco Fantin, Armenio C. Serra, Jorge F. J. Coelho
Summary: In this study, the aqueous photoinduced ICAR ATRP of acrylamide was successfully scaled up from small-scale to large-scale. By optimizing the reaction conditions, this method can efficiently and feasibly produce a large quantity of polyacrylamide.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Polymer Science
Andreia S. R. Oliveira, Patricia Pereira, Patricia V. Mendonca, Ana C. Fonseca, Sergio Simoes, Armenio C. Serra, Jorge F. J. Coelho
Summary: This work focuses on the controlled synthesis of amphiphilic biodegradable block copolymers (BCPs) and investigates their self-assembly behavior in aqueous solution. The BCPs demonstrated the ability to form micelles and degrade under physiological conditions, making them promising materials for drug/gene delivery.
Article
Biochemistry & Molecular Biology
Daniela Santo, Rosemeyre A. Cordeiro, Patricia V. Mendonca, Armenio C. Serra, Jorge F. J. Coelho, Henrique Faneca
Summary: Cationic glycopolymers have shown great potential as gene delivery systems due to their biocompatibility and binding affinity to specific receptors. However, their synthesis process is complicated, and they have solubility issues. In this study, a mini-library of well-defined poly(2-aminoethyl methacrylate hydrochloride-co-poly(2-lactobionamidoethyl methacrylate) (PAMA-co-PLAMA) glycopolymers was synthesized using ARGET ATRP. The generated glycoplexes demonstrated high specificity and efficiency in gene delivery, and when combined with small amounts of docetaxel, they showed potent antitumor activity in HCC models.
Article
Pharmacology & Pharmacy
Daniela Santo, Patricia V. Mendonca, Armenio C. Serra, Jorge F. J. Coelho, Henrique Faneca
Summary: This study developed a lactobionic acid-based gene delivery nanosystem to downregulate c-MYC expression and sensitize tumor cells to sorafenib. The nanocarriers prepared with PAMA114-co-PLAMA20 glycopolymer showed the most efficient gene delivery. Silencing c-MYC increased the sensitivity of HCC cells to sorafenib, demonstrating the potential of PAMA114-co-PLAMA20/MYC shRNA nanosystems combined with low doses of sorafenib for HCC treatment.
INTERNATIONAL JOURNAL OF PHARMACEUTICS
(2023)
Article
Biochemistry & Molecular Biology
Carlos T. B. Paula, Ana Leandro, Patricia Pereira, Jorge F. J. Coelho, Ana C. Fonseca, Armenio C. Serra
Summary: This study proposes the development of an injectable, fast-gelling hydrogel that can change its mechanical properties upon exposure to light. The hydrogels show fast gelation time, good swelling ability, and cell compatibility, making them a potential material for burn wound treatment.
MACROMOLECULAR BIOSCIENCE
(2023)
Correction
Polymer Science
Andreia S. R. Oliveira, Patricia Pereira, Patricia V. Mendonca, Ana C. Fonseca, Sergio Simoes, Armenio C. Serra, Jorge F. J. Coelho
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
