Review
Chemistry, Physical
Chang-Qing Qin, Cheng Zhao, Guo-Shu Chen, Yun-Lin Liu
Summary: Catalytic enantioselective azide-alkyne cycloaddition (E-AAC) is an efficient technology for constructing diverse chiral triazoles, with applications in synthetic and medicinal chemistry, biological chemistry, and materials science. Significant developments have been made in copper-, nickel-, iridium-, and rhodium-catalyzed E-AAC reactions in the past six years. This review summarizes these advancements according to different strategies implemented.
Article
Chemistry, Multidisciplinary
Suguru Yoshida, Yuki Sakata, Yoshihiro Misawa, Takamoto Morita, Tomoko Kuribara, Harumi Ito, Yuka Koike, Isao Kii, Takamitsu Hosoya
Summary: Efficient consecutive formation of 1,2,3-triazoles using multiazide platforms has been achieved in this study. A four-step synthesis of tetrakis(triazoles) was successfully performed from a tetraazide platform molecule, based on the unique clickability of the 1-adamantyl azido group. This method was applied to the convergent synthesis of tetrafunctionalized probes in a modular synthetic manner.
CHEMICAL COMMUNICATIONS
(2021)
Review
Biotechnology & Applied Microbiology
Priyank Purohit, Akanksha Bhatt, Ravi K. Mittal, Magda H. Abdellattif, Thoraya A. Farghaly
Summary: Polymer grafting is a technique to improve the morphology and properties of polymers. By creating copolymers or grafting, the physicochemical properties of polymers can be further modified. This review discusses various chemical approaches for polymer grafting, such as free radical reactions, click reactions, amide formation, and alkylation. The review also covers the importance of the graft-to approaches and their application in different fields.
FRONTIERS IN BIOENGINEERING AND BIOTECHNOLOGY
(2023)
Article
Biology
Z. Soederlund, A. Ibanez-Fonseca, S. Hajizadeh, J. C. Rodriguez-Cabello, J. Liu, L. Ye, E. Tykesson, L. Elowsson, G. Westergren-Thorsson
Summary: The study demonstrates the application of synthetic glycosaminoglycans in inducing desired cellular responses and the possibility of specific growth factor release using a modular 3D scaffold in vitro and in vivo.
COMMUNICATIONS BIOLOGY
(2022)
Article
Chemistry, Organic
T. Moritz Weber, Joerg Pietruszka
Summary: Copper-catalyzed alkyne azide click chemistry (CuAAC) is important for drug development and biological materials labeling. A new tridentate Cu-ligand called TDETA was synthesized as a scalable and non-toxic alternative to HN3 and the previously used DTEA ligand. TDETA showed excellent solubility in organic solvents and aqueous solutions, outcompeted commercial ligands THPTA and TBTA for various azide and alkyne combinations using Cu(I) and Cu(II) species, and had a 80% recovery yield.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Borja Cirera, Alexander Riss, Pingo Mutombo, Jose Urgel, Jose Santos, Marco Di Giovannantonio, Roland Widmer, Samuel Stolz, Qiang Sun, Max Bommert, Roman Fasel, Pavel Jelinek, Willi Auwarter, Nazario Martin, David Ecija
Summary: The design of organometallic complexes is crucial in modern organic chemistry and catalysis. On-surface synthesis has recently emerged as a disruptive method to design compounds and nanomaterials previously considered impossible. The activation of inner diacetylene moieties of a molecular precursor by copper surface adatoms has led to the formation of unprecedented organocopper metallacycles on Cu(111), paving the way for new avenues in organometallic compound engineering and polyyne chemistry on surfaces.
Article
Chemistry, Applied
Shaik Syed Hussain, Kesavarao Sykam, Ramanuj Narayan, Pratyay Basak
Summary: Si-PUTs were prepared by azide-alkyne cycloaddition, showing excellent surface hydrophobicity and anti-corrosion properties. A simple modification of aminopropyl trimethoxy silane produced a dialkyne terminated monomer, while azide-terminated urethane monomers were synthesized using azidoethanol and common diisocyanates. The successful formation of Si-PUTs was confirmed by FTIR and XPS analysis, and their performance as corrosion resistive coatings was evaluated comprehensively.
PROGRESS IN ORGANIC COATINGS
(2023)
Article
Chemistry, Physical
Ge Yang, Yali Xie, Yaru Wang, Ying Tang, Leng Leng Chng, Fuyi Jiang, Fanglin Du, Xianfeng Zhou, Jackie Y. Ying, Xun Yuan
Summary: This paper reports on the design of a novel Cu-based nanocatalyst, watersoluble thiolated Cu-30 nanoclusters (NCs), for living cell labeling via CuAAC. The Cu-30 NCs exhibit good biocompatibility, excellent stability, and scalable synthesis, making them a promising catalyst for potential commercial applications. Furthermore, the Cu-30 NCs demonstrate superior catalytic activities for a series of Huisgen cycloaddition reactions with good recyclability, making them suitable for intracellular bioorthogonal applications.
Article
Chemistry, Organic
Yulia Krivolapova, Olesya A. Tomashenko, Liya D. Funt, Dar'ya Spiridonova, Mikhail S. Novikov, Alexander F. Khlebnikov
Summary: Azirine-triazole hybrids were selectively synthesized under different reaction conditions and the reaction mechanism and selectivity were discussed based on DFT calculations.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Correction
Chemistry, Inorganic & Nuclear
Firdaus Rahaman Gayen, Abdul Aziz Ali, Debashree Bora, Saptarshi Roy, Supriya Saha, Lakshi Saikia, Rajib Lochan Goswamee, Biswajit Saha
Summary: This study focuses on the synthesis and characterization of a ferrocene functionalized Schiff base containing Cu(II) complex, and demonstrates its catalytic activity in the azide alkyne cycloaddition reaction at parts-per-million levels.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Cecilia Garcia-Oliva, Alejandro Merchan, Almudena Perona, Pilar Hoyos, Angel Rumbero, Maria J. Hernaiz
Summary: Two green strategies, solvent free mechanochemistry and microwave irradiation using a recycable biosolvent, based on two activation pathways, for copper-catalyzed azide-alkyne cycloaddition reaction were reported. Glucuronic acid glycodendrimers were synthesized with good conversions (99%), with the microwave pathway being the ideal tool (90% yield in 90 min).
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Cong Guan, Jiabin Yin, Jian Ji, Jinhua Liu, Xiang Wu, Tong Zhu, Shunying Liu
Summary: A regioselective electrochemical C-H amination method using easily accessible ethers has been developed to synthesize N (2)-substituted 1,2,3-triazole. Multiple substituents, including heterocycles, were well-tolerated, and 24 examples were obtained in moderate to good yields. Control experiments and DFT calculations revealed that the electrochemical synthesis occurs through a N-tosyl 1,2,3-triazole radical cation process, promoted by single-electron transfer from the lone pair electrons of the aromatic N-heterocycle, and the desulfonation is responsible for the high N (2)-regioselectivity.
Article
Agricultural Engineering
Huazhong Ma, Jianglin Zhao, Ying Liu, Liang Liu, Juan Yu, Yimin Fan
Summary: An interpenetrating network (IPN) hydrogel was developed by crosslinking nanocellulose and sodium alginate through an acetic acid coagulation bath and Ca2+ chelation. The nanofibers in the hydrogel greatly extended the release time of aspirin to 60 hours, thanks to the well-structured network. Carboxyl groups played a role in the release capacity in different pH environments. This study provides a guide for the preparation of physically crosslinked IPN hydrogels with good mechanical properties and cytocompatibility for drug delivery applications.
INDUSTRIAL CROPS AND PRODUCTS
(2023)
Article
Biochemistry & Molecular Biology
D. Pal Manisha, Ruchi Chawla, Pradip Kumar Dutta
Summary: A calcium-chitosan-triazole nanocomplex (Ca@CS-Tz) was synthesized using calcium carbide (CaC2) as a source of acetylene. The nanocomplex showed efficient drug delivery, antimicrobial activity against bacteria and fungi, and significant antioxidant property. Targeted drug release experiments were conducted and the nanocomplex demonstrated high release efficiency at pH 5.0 and 7.4. The results were compared with a previously reported chitosan triazole derivative.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2023)
Article
Chemistry, Applied
Hakimeh Mirzaei, Hossein Eshghi, Seyed Mohammad Seyedi
Summary: The copper immobilized on silk fibroin was successfully prepared and characterized using multiple techniques, showing good catalytic activity in the azide-alkyne cycloaddition reaction under mild conditions. The heterogeneous-supported Cu catalyst showed stable catalytic activity after being reused four times.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Friedrich Stricker, David M. Sanchez, Umberto Raucci, Neil D. Dolinski, Manuel S. Zayas, Jan Meisner, Craig J. Hawker, Todd J. Martinez, Javier Read de Alaniz
Summary: This study reports a novel photoswitch that can independently control multiple molecular states, enabling the transformation of a three-stage photoswitch to be controlled by regulating intermediates along the reaction pathway.
Article
Chemistry, Physical
Xiaoen Wang, Cheng Zhang, Michal Sawczyk, Qinghong Yuan, Fangfang Chen, Tiago C. Mendes, Patrick C. Howlett, Changkui Fu, Petr Kral, Craig J. Hawker, Andrew Whittaker, Maria Forsyth, Ju Sun, Yiqing Wang, Xiao Tan, Debra J. Searles
Summary: This study developed solvent-free solid polymer electrolytes for safe and stable all-solid-state sodium metal batteries, demonstrating excellent cycling performance and charge/discharge stability. Sodium metal batteries show promising application prospects in energy storage systems.
Article
Chemistry, Multidisciplinary
Allison L. Chau, Patrick T. Getty, Andrew R. Rhode, Christopher M. Bates, Craig J. Hawker, Angela A. Pitenis
Summary: This study investigates the tribological properties of P(AAm-co-AA) hydrogels and finds that tunable lubricity is related to the protonation state of acrylic acid and electrostatic interactions.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Robert D. Murphy, Ronnie V. Garcia, Seung J. Oh, Tanner J. Wood, Kyoo D. Jo, Javier Read de Alaniz, Ed Perkins, Craig J. Hawker
Summary: Describes the synthesis of functional hydrogels from 3-arm diblock copolypeptide stars, which achieve mechanical stability and biological activity through physical and photo-crosslinking, enabling direct ink writing of 3D objects with high precision and biological viability.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Junfeng Chen, Aoon Rizvi, Joseph P. Patterson, Craig J. Hawker
Summary: This study reports a method to prepare libraries of discrete PEG analogues with a branched, nonlinear structure, which can achieve efficient nanoparticle assembly while reducing antibody recognition. The results illustrate the advantages of discrete macromolecules in terms of improved properties and reduced antibody responses.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Materials Science, Composites
Younghoon Kwon, Soyoung E. Seo, Jaejun Lee, Szabolcs Berezvai, Javier Read de Alaniz, Claus D. Eisenbach, Robert M. McMeeking, Craig J. Hawker, Megan T. Valentine
Summary: Additive manufacturing allows the creation of bio-inspired materials with complex architectures and diverse properties. By using a digital light processing strategy, polymer foams with controlled porosity were 3D printed by incorporating thermally expandable microspheres. The foams showed remarkable resilience under cyclic loading, maintaining their modulus and energy dissipation even at large deformations.
COMPOSITES COMMUNICATIONS
(2023)
Article
Polymer Science
Oscar Nordness, Joshua D. Moon, Nico Marioni, Everett S. Zofchak, Peter M. Richardson, Matthew R. Landsman, Lynn E. Katz, Craig J. Hawker, Venkat Ganesan, Rachel A. Segalman, Raphaele J. Clement
Summary: The effects of ligand basicity on water and ion transport within hydrogel membranes are investigated using a library of functionalizable poly(ethylene glycol) diacrylate (PEGDA) polymer networks. The study reveals that the self-diffusion of water molecules and ions is primarily driven by the hydration level of the membrane. The interaction between triflate anions and the polymer significantly reduces ion and water mobility.
Article
Polymer Science
KaitlinR. Albanese, Yoichi Okayama, Parker T. Morris, Matthias Gerst, Rohini Gupta, Joshua C. Speros, Craig J. Hawker, Chungryong Choi, Javier Read de Alaniz, Christopher M. Bates
Summary: We report a strategy to create degradable poly(acrylate) pressure-sensitive adhesives (PSAs) using 1,2-dithiolanes as drop-in replacements for traditional acrylate comonomers. The resulting PSA materials have comparable thermal and viscoelastic properties to nondegradable analogues, but can undergo reversible transformation between high and low molecular weights through oxidative repolymerization and reductive degradation. This simple and versatile chemistry could play a pivotal role in improving the sustainability of contemporary adhesives.
Article
Chemistry, Multidisciplinary
Robert D. Murphy, Colm Delaney, Srikanth Kolagatla, Larisa Florea, Craig J. Hawker, Andreas Heise
Summary: This study reports the design of photopolymerizable copolypeptides with tailored mechanical properties for additive manufacturing of 3D objects. The copolypeptides are able to form hydrogels suitable for direct ink writing or direct laser writing, leading to mechanically robust 3D structures.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Polymer Science
Yoichi Okayama, Taejun Eom, Michael Czuczola, Allison Abdilla, Jacob R. Blankenship, Kaitlin R. Albanese, Javier Read de Alaniz, Christopher M. Bates, Craig J. Hawker
Summary: The synthetic utility of heterotelechelic polydimethylsiloxane (PDMS) derivatives was enhanced by using a specifically designed silyl hydride (Si-H)-based initiator for anionic ring-opening polymerization (AROP) of hexamethylcyclotrisiloxane (D-3) monomers. The resulting PDMS polymers had high chain-end fidelity and heterotelechelic functionality. In situ termination of the propagating chain end with different chlorosilanes and functionalized alkenes further increased the diversity of the PDMS derivatives. The living nature of the polymerization allowed for the synthesis of narrow-dispersity polymers with a wide range of molar masses. Additionally, the feasibility of synthesizing supersoft bottlebrush networks using the PDMS macromonomers was demonstrated.
Article
Polymer Science
Gervase Ng, Zilong Wu, Tong Zhang, Anh Phong Dang, Yin Yao, Andrew R. J. Nelson, Stuart W. Prescott, Almar Postma, Graeme Moad, Craig J. Hawker, Cyrille Boyer
Summary: An oxygen-tolerant SI-PhotoRAFT technique has been developed for efficient synthesis of surface-tethered polymer brushes under low-energy near-infrared light. The technique takes advantage of the unique properties of NIR light to prepare polymeric coatings, even through barriers that are opaque to visible light. It enables precise modulation of brush height and sequential chain extension, as well as orthogonal control over polymerization and cross-linking processes using two different wavelengths.
Article
Chemistry, Multidisciplinary
Ronnie V. Garcia, Elizabeth A. Murphy, Nairiti J. Sinha, Yoichi Okayama, Juan Manuel Uruena, Matthew E. Helgeson, Christopher M. Bates, Craig J. Hawker, Robert D. Murphy, Javier Read de Alaniz
Summary: Shear-recoverable hydrogels with rapid self-recovery based on block copolypeptides have the potential to be used in extrudable and injectable 3D-printing applications. By synthesizing 3-arm star-shaped block copolypeptides with different side chains and block lengths, hydrogels with diverse microstructures and mechanical properties are prepared. The study reveals that non-canonical & beta;-sheet blocks based on phenyl glycine form more stable networks with superior mechanical properties and writability compared to natural amino acid counterparts.
Article
Polymer Science
Colton A. D'Ambra, Michael Czuczola, Patrick T. Getty, Elizabeth A. Murphy, Allison Abdilla, Souvagya Biswas, Jodi M. Mecca, Thomas D. Bekemeier, Steven Swier, Craig J. Hawker, Christopher M. Bates
Summary: A versatile synthetic platform is reported for the synthesis of high molecular weight graft copolymers with excellent control over molecular weight and grafting density. The controlled nature of side-chain growth is confirmed by selective degradation of the siloxane backbone, and grafting density and functionality can be further controlled by using a mixture of thiols.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Polymer Science
Kaitlin R. Albanese, Jacob R. Blankenship, Timothy Quah, Amy Zhang, Kris T. Delaney, Glenn H. Fredrickson, Christopher M. Bates, Craig J. Hawker
Summary: The potential of ABC triblock terpolymers in improving the mechanical properties of thermoplastic elastomers is demonstrated by comparing them with symmetric ABA/CBC analogs having similar molecular weights and volume fraction of B and A/C domains. The ABC architecture enhances elasticity through full chain bridging between discrete hard domains, minimizing mechanically unproductive loops. In addition, ABC triblock terpolymers allow for a higher fraction of hard-block domains while maintaining elasticity, which is traditionally only possible with non-linear architectures or highly asymmetric ABA triblock copolymers. These advantages provide a tunable platform to create materials with practical applications while improving our fundamental understanding of chain conformation and structure-property relationships in block copolymers.
Review
Nanoscience & Nanotechnology
Yiqing Wang, Zhenzhen Wu, Faezeh Makhlooghi Azad, Yutong Zhu, Lianzhou Wang, Craig J. Hawker, Andrew K. Whittaker, Maria Forsyth, Cheng Zhang
Summary: The incorporation of fluorine into battery components can improve the energy density, safety, and cycling stability of rechargeable batteries. This review explores the design and utilization of fluorine-containing species in advanced batteries, examining the relationship between their chemical structure and battery performance. It also discusses the challenges and opportunities of fluorinated batteries within the present regulatory framework.
NATURE REVIEWS MATERIALS
(2023)
