Review
Chemistry, Multidisciplinary
Mohamed Dergham, Shanmeng Lin, Jin Geng
Summary: In cellulo supramolecular self-assembly, based on non-covalent forces, provides an accurate and controllable method to regulate cell properties and biological functions. It utilizes host-guest interactions, pH changes, enzymes, and polymerization-induced self-assembly to induce various unnatural reactions without disrupting natural biological processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Catriona C. James, Bas de Bruin, Joost N. H. Reek
Summary: The importance of transition metal catalysis lies in its wide range of applications, including the synthesis of chemicals, natural products, and pharmaceuticals. However, a relatively new application is the catalysis of new-to-nature reactions inside living cells. The complex environment of living cells poses challenges to transition metal catalysts due to the potential inhibition or deactivation by various biological components. In this review, we summarize the current progress in the field of transition metal catalysis, focusing on the evaluation of catalysis efficiency under living cell and biological conditions. Catalyst poisoning is a common issue in this field, and we suggest that future research should explore physical and kinetic protection strategies to enhance the reactivity of catalysts in cells.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Liyang Fu, Yanxue Che, Yanjun Gong, Hongwei Ji, Yifan Zhang, Ling Zang, Jincai Zhao, Yanke Che
Summary: We report a tunable 2D living self-assembly method for controlling the geometric shape variety and mechanical properties of uniform 2D platelets. The approach involves using n-alkyl alcohols to form a 2D network via hydrogen bonding, resulting in three effects: maintaining the same optical properties and thermal stability, generating alcohol-dependent 2D shape variety, and varying the mechanical properties through the interactions of different alcohol tail lengths.
CHEMISTRY OF MATERIALS
(2023)
Article
Polymer Science
Chloe Grazon, Pedro Salas-Ambrosio, Segolene Antoine, Emmanuel Ibarboure, Olivier Sandre, Andrew J. Clulow, Ben J. Boyd, Mark W. Grinstaff, Sebastien Lecommandoux, Colin Bonduelle
Summary: Polymerization-induced self-assembly (PISA) is an efficient one-step process to obtain nanomaterials. ROPISA using aqueous ring-opening polymerization of alpha-amino acid N-carboxyanhydride yields well-defined nanoassemblies. The secondary structure of the polypeptides is the main driving force in stabilizing the anisotropic rod-like nanostructures.
Article
Chemistry, Multidisciplinary
Yingtong Zong, Si-Min Xu, Wenying Shi, Chao Lu
Summary: This article describes a chiral supramolecular assembly (CSA) based on achiral molecules, which provides important clues for understanding the origin of biological chirality. By utilizing the two-dimensional confined space of layered double hydroxide (LDH), simple achiral molecules can be arranged into staggered bilayer structures, forming non-mirror image chiral supramolecular isomers (CSIs). This strategy breaks the stereotype that complex molecular structures and symmetry breaking mechanisms are necessary for the formation of detectable CSA by achiral molecules.
Article
Chemistry, Multidisciplinary
Violeta Vazquez-Gonzalez, Maria J. Mayoral, Fatima Aparicio, Paula Martinez-Arjona, David Gonzalez-Rodriguez
Summary: Nanotubes, a fascinating self-assembled structure in supramolecular chemistry, can be produced from dinucleobase monomers through cyclotetramerization and supramolecular polymerization. The role of peripheral amide groups in guiding the polymerization process and their influence on the stabilization of macrocycles and the polymerization mechanism have been quantitatively analyzed using H-1 NMR and CD spectroscopy techniques.
Article
Multidisciplinary Sciences
Joseph F. Woods, Lucia Gallego, Amira Maisch, Dominik Renggli, Corrado Cuocci, Olivier Blacque, Gunther Steinfeld, Andres Kaech, Bernhard Spingler, Andreas Vargas Jentzsch, Michel Rickhaus
Summary: This study demonstrates that the process of shape-assisted self-assembly is consistent across various derivatives, highlighting the restriction of rotational motion. This finding is important for precise molecular self-assembly and the generation of new materials.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Yanjun Gong, Chuanqin Cheng, Hongwei Ji, Yanke Che, Ling Zang, Jincai Zhao, Yifan Zhang
Summary: Uniform two-dimensional platelets with tailorable shapes and controlled sizes are successfully constructed by creating new nuclei from a donor-acceptor molecule and 1-hexanol in this study. The growth of these platelets can be regulated by simply varying the amount of 1-hexanol, and complex concentric multiblock 2D heteroplatelets can be obtained by sequential and alternative addition of different donor-acceptor molecules. These platelets exhibit enhanced photostability compared to those obtained by conventional self-assembly without 1-hexanol involvement.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Polymer Science
Shixing Lei, Jia Tian, Tomoya Fukui, Mitchell A. Winnik, Ian Manners
Summary: This study experimentally investigated the growth of one-dimensional fiber-like structures and found that there was no significant correlation between fiber length and growth rate. This suggests that the low size dispersities characteristic of living crystallization-driven self-assembly processes do not result from a gradual reduction in growth rate with fiber length, supporting the previously proposed explanation based on an analogy with living covalent polymerizations of molecular monomers.
Article
Chemistry, Multidisciplinary
Nicolas M. Casellas, Lorenzo Albertazzi, Silvia Pujals, Tomas Torres, Miguel Garcia-Iglesias
Summary: In this study, a designed and synthesized amine functionalized C-3-symmetric benzotrithiophene (BTT) monomer was used to form pH responsive one-dimensional supramolecular polymers in aqueous media. Instead of simply looking at the effect of pH on aggregate size, a detailed mechanistic study was carried out, revealing a dramatic and reversible change in polymerization mechanism and supramolecular fiber size by modifying pH to induce formation of positively charged ammonium groups. This change was attributed to Coulombic repulsive forces and higher monomer solubility, and was further utilized to control one-dimensional supramolecular polymerization and copolymerization processes through induced frustrated growth of fibers.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Polymer Science
Tian Zhang, Eamonn D. Conrad, Derek P. Gates
Summary: The living anionic polymerization of phosphaalkene has been used to synthesize a series of PMP homopolymers and PMP/S block copolymers. The samples showed monodispersity, narrow dispersities, and specific transition temperatures in their DSC chromatograms.
Article
Chemistry, Multidisciplinary
Kae Yamashita, Munenori Numata
Summary: This study presents a basic microflow system for multistep supramolecular polymerization. The system allows for injection of monomer, directional supramolecular copolymerization, removal of unreacted monomer, and purification of the product supramolecular diblock copolymers along a three-stream flow. The study demonstrates the selective reaction at the forward-facing terminus of the supramolecular polymer, leading to high-purity supramolecular diblock copolymers.
Review
Chemistry, Multidisciplinary
Xiangyang Zhang, Junxia Wang, Ying Zhang, Zhimou Yang, Jie Gao, Zhen Gu
Summary: Living organisms fabricate biomacromolecules such as DNA, RNA, and proteins through self-assembly, and understanding this process has led to exploration in synthesizing biomaterials within living organisms. In recent decades, these in vivo synthesized biomaterials have been extensively applied in cell-fate manipulation, disease theranostics, bioanalysis, cellular surface engineering, and tissue regeneration.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Jeong Sang Oh, Ka Young Kim, Minhye Kim, Sukyoung Kim, Sung Ho Jung, Jong Hwa Jung
Summary: We synthesized chiral supramolecular tri- and penta-BCPs with controllable chirality using a kinetically adjusted seeded supramolecular copolymerization method in THF and DMSO. Tetraphenylethylene derivatives with alanine side chains formed thermodynamically favored chiral products, while achiral TPE-G with glycine moieties did not form a supramolecular polymer due to energy barrier. However, copolymerization of the metastable states of TPE-G allowed the generation of supramolecular BCPs and transfer of chirality.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Xiaoping Wang, Mao Quan, Huan Yao, Xin-Yu Pang, Hua Ke, Wei Jiang
Summary: The authors report a pair of water-soluble naphthotubes with a pH-responsive cavity for switchable bifunctional recognition in water. These hosts have a switchable cavity and can be used for the construction of smart self-assembly systems and water-soluble molecular machines.
NATURE COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Vakayil K. Praveen, Balaraman Vedhanarayanan, Arindam Mal, Rakesh K. Mishra, Ayyappanpillai Ajayaghosh
ACCOUNTS OF CHEMICAL RESEARCH
(2020)
Article
Chemistry, Multidisciplinary
Arindam Mal, Samiyappan Vijayakumar, Rakesh K. Mishra, Jubi Jacob, Renjith S. Pillai, B. S. Dileep Kumar, Ayyappanpillai Ajayaghosh
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Anjali Nirmala, Indulekha Mukkatt, Sreejith Shankar, Ayyappanpillai Ajayaghosh
Summary: The study demonstrates a method to use a mixture of iron (II) chloride and bipyridine as a reversible thermochromic switch and logic operator, showing generality. It also proves the concept of an optically readable multi-state volatile memory with temperature as a precision input.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Nanoscience & Nanotechnology
Indulekha Mukkatt, Anjali Nirmala, Nayan Dev Madhavan, Sreejith Shankar, Biswapriya Deb, Ayyappanpillai Ajayaghosh
Summary: The study designed three tetraterpyridine ligands with variations in their core architecture to create spray-coated electrochromic assemblies of iron(II)-based metallosupramolecular polymer network films. These assemblies exhibited high coloration efficiencies and optical contrast, suitable for electrochromic devices. The ligand-structure induced differential metal coordination led to porosity and spectroelectrochemical diversification, enabling the creation of electrochromic patterns and images through a simple spray-coating technique.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Gourab Das, Sandeep Cherumukkil, Akhil Padmakumar, Vijay B. Banakar, Vakayil K. Praveen, Ayyappanpillai Ajayaghosh
Summary: In this study, the creation and control of distinct supramolecular energy landscapes for reversible control of excited-state emission processes were demonstrated through cascade energy transfer in chromophore assemblies. Enhanced near-infrared emission was achieved by manipulating morphology and excitation energy transfer with variable solvent composition and ultrasound stimulation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sandeep Cherumukkil, Gourab Das, Ravi P. N. Tripathi, G. V. Pavan Kumar, Sunil Varughese, Ayyappanpillai Ajayaghosh
Summary: Bodipy-PE-2 self-assembly forms a layered photonic structure upon thermal annealing, exhibiting angle-dependent iridescence of green and pink with a luminescence shift from yellow to red. The properties are attributed to the micro- and nano-periodicity associated with the layered structure and the phase transformation due to annealing. The material shows active and passive waveguiding properties when excited with 532 and 633 nm laser sources.
ADVANCED FUNCTIONAL MATERIALS
(2022)
Article
Chemistry, Physical
C. K. Vipin, Atul Shukla, Kavya Rajeev, Monirul Hasan, Shih-Chun Lo, Ebinazar B. Namdas, Ayyappanpillai Ajayaghosh, K. N. Narayanan Unni
Summary: Pure white light emission was achieved by combining the exciplex emission with field-induced electromer emission. Electromer emission has significantly long-lived components, indicating possible utilization of triplet excitons in radiative recombination.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Materials Science, Multidisciplinary
Anjali K. Sajeev, Nishkarsh Agarwal, Anjaly Soman, Shilpi Gupta, Monica Katiyar, A. Ajayaghosh, K. N. Narayanan Unni
Summary: The study demonstrates the use of an external light extraction layer made of polydimethylsiloxane and zinc oxide nanoparticles to enhance the efficiency of OLEDs. The layer significantly improves light outcoupling, with white OLEDs showing the highest enhancement of 80%. Green OLEDs also exhibit substantial improvement, followed by red and blue OLEDs.
ORGANIC ELECTRONICS
(2022)
Article
Chemistry, Multidisciplinary
Avinash Dhamija, Chandan K. Das, Young Ho Ko, Younghoon Kim, Rahul Dev Mukhopadhyay, Anilkumar Gunnam, Xiujun Yu, In-Chul Hwang, Lars Schaefer, Kimoon Kim
Summary: This study reports the construction of a supramolecular rotor in a porous Zn-metallated porphyrinic cage and the control of its dual motions by external stimuli, which has important potential applications.
Review
Chemistry, Multidisciplinary
Rahul Dev Mukhopadhyay, Ayyappanpillai Ajayaghosh
Summary: Metallo-supramolecular polymers have gained attention and development in the field of soft materials due to their well-defined topologies and dynamic metallosupramolecular interactions. These stimuli-responsive supramolecular structures have potential applications in optoelectronic device fabrication, but challenges remain in developing systems with offbeat applications and achieving precise control. Controlling the morphology of these soft materials also presents challenges. This review discusses recent developments and future directions, including synthetic methodologies and programmed synthesis techniques, for constructing stimuli-responsive metallosupramolecular systems.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Materials Science, Multidisciplinary
Reethu Haridas, Jayadev Velore, Sourava Chandra Pradhan, Asarikal Vindhyasarumi, Karuvath Yoosaf, Suraj Soman, K. N. Narayanan Unni, Ayyappanpillai Ajayaghosh
Summary: Two new molecularly engineered D-pi-A sensitizers, YK 8 and YK 9, based on carbazole have been developed for indoor photovoltaic applications. The efficient power output achieved under various illumination conditions demonstrates the potential of these sensitizers for powering low-power sensors and actuators on the Internet of Things network. The study also explores the role of pi-spacer in recombination and device performance through extensive interfacial studies.
MATERIALS ADVANCES
(2021)
Article
Materials Science, Multidisciplinary
Sarah K. M. McGregor, Chinju Govind, Michael K. R. Wood, Atul Shukla, Hyunsoo Lim, Romain J. Lepage, Elizabeth H. Krenske, Narayanan K. N. Unni, Ayyappanpillai Ajayaghosh, Venugopal Karunakaran, Ebinazar B. Namdas, Shih-Chun Lo
Summary: A new solution-processable N-styrylcarbazole-linked tetraphenylethylene derivative with green-orange emission was synthesized and characterized, showing significant photoluminescence enhancement in neat-film. The excited-state dynamics and enhanced PLQYs in the solid state were attributed to the restriction of structural relaxations, not aggregation effects commonly associated with TPE materials.
ADVANCED PHOTONICS RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Sandip Chakraborty, Manu M. Joseph, Sunil Varughese, Samrat Ghosh, Kaustabh K. Maiti, Animesh Samanta, Ayyappanpillai Ajayaghosh
Article
Chemistry, Multidisciplinary
I Mukkatt, P. M. Anjana, A. Nirmala, R. B. Rakhi, S. Shankar, A. Ajayaghosh
MATERIALS TODAY CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Samrat Ghosh, Sreejith Shankar, Divya Susan Philips, Ayyappanpillai Ajayaghosh
MATERIALS TODAY CHEMISTRY
(2020)
