Article
Chemistry, Multidisciplinary
Yuting Bi, Caikun Cheng, Zongze Zhang, Rongjuan Liu, Jingjing Wei, Zhijie Yang
Summary: In this work, the authors demonstrate the coupling of molecular self-assembly kinetics with the colloidal self-assembly kinetics of inorganic nanoparticles, leading to the formation of hierarchically assembled tubular nanocomposites with distinct structures. By serving as artificial histones, the colloidal nanoparticles promote the formation of single layered nanotubes and resistant tubular nanocomposites. Alternatively, aggregated nanoparticles are encapsulated into double-layer supramolecular nanotubes, resulting in nanoparticle superlattices with open channels. Increasing the amounts of nanoparticles enables the assembly into pseudohexagonal superlattices and triple-layered tubular nanocomposites. The sense of helicity transfers from the supramolecular nanotubes to the nanoparticle superlattices. These findings provide a strategy for designing and controlling hierarchical assembly between supramolecular chemistry and inorganic solids.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Engineering, Biomedical
Eduardo Anaya-Plaza, Ahmed Shaukat, Inka Lehtonen, Mauri A. Kostiainen
Summary: The strategy of combining biomolecules and synthetic components to develop biohybrids is becoming increasingly popular for preparing highly customized and biocompatible functional materials， allowing the excellent properties of carbon nanotubes (CNTs) to be applied to biomedical applications. The resulting well-defined composites of CNTs conjugated with relevant biomolecules enable the exploitation of nanoscale properties at the micro- and macroscale, with potential applications in tissue engineering, sensors, and wearable electronics. This review presents the underlying chemistry behind the CNT-based biohybrid materials and discusses the future directions of the field.
ADVANCED HEALTHCARE MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Yunlong Zhang, Donglei Yang, Pengfei Wang, Yonggang Ke
Summary: Structural DNA nanotechnology enables the fabrication of designer nanoscale artificial architectures. In this study, we developed a molecular assembly system where DNA tiles can assemble into tubes and then large one-dimensional DNA bundles. By incorporating a cohesive link into the tiles, we induced intertube binding and successfully formed DNA bundles with micrometer-length and nanometer-width, whose assembly was collectively determined by cationic strength and linker designs. Moreover, programmable spatial features and compositions of multicomponent DNA bundles were realized. Lastly, dynamic capability was implemented to achieve reversible reconfigurations among tile, tube, and bundles. This assembly strategy expands the toolbox of DNA nanotechnology and has broad applications in materials science, synthetic biology, biomedical science, and beyond.
Review
Chemistry, Multidisciplinary
Ling Bai, Ning Wang, Yuliang Li
Summary: Organic semiconductors (OSs) are currently utilized as active components in various practical devices, with design strategies combining organic synthetic chemistry and supramolecular assembly technology playing a crucial role in the development of a new generation of multiscale OSs. These strategies aim to satisfy the requirements of different devices by controlling the morphology and properties of multiscale OS components from nanometers to macroscopic micrometers. Various design strategies have been comprehensively reviewed, with discussions on applications in practical devices and future research directions.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Katarina Gvozden, Sanja Novak Ratajczak, Alberto G. Orellana, Emmanuel Kentzinger, Ulrich Rucker, Jan K. G. Dhont, Cristiano De Michele, Emmanuel Stiakakis
Summary: Stiff DNA fragments can self-assemble into various smectic mesophases in concentrated aqueous solutions by selectively screening blunt-end DNA stacking interactions. The strength of attractions can be controlled to stabilize different phases, demonstrating the potential for precise tuning of DNA blunt-ends as monovalent attractive patches in the assembly of nonconventional DNA-based liquid crystal phases.
Article
Chemistry, Multidisciplinary
Jie Xu, Changzhu Lv, Qiangqiang Shi, Jialin Zhang, Ning Wang, Guoying Zhang, Jinming Hu, Shiyong Liu
Summary: Discrete polymers are a valuable tool for studying chain structure, self-assembly behavior, and functional applications. However, the development of discrete polymers with self-immolative properties is limited. In this study, we synthesized a library of self-immolative oligourethanes through stepwise growth, which exhibited cascade depolymerization and selective cleavage properties. These oligourethanes also displayed different morphologies and morphological transitions in aqueous media and upon thermal annealing.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Baipeng Yin, Wubin Wu, Chenghu Dai, Hao Jia, Chuang Zhang, Jiannian Yao
Summary: A general approach for assembling colloidal microspheres into coupled microcavities using magnetostatic interactions under an external field has been reported. By designing the local field gradient around microspheres, virtual templates can be formed to produce various coupled photonic structures. This method shows promise for easily and efficiently fabricating coupled microstructures for photonic and optoelectronic applications.
ADVANCED FUNCTIONAL MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Bryan H. H. Ferlez, Henning Kirst, Basil J. J. Greber, Eva Nogales, Markus Sutter, Cheryl A. A. Kerfeld
Summary: Many bacteria use bacterial microcompartments (BMCs) to organize enzymatic reactions. Shell proteins derived from BMCs can self-assemble into various structures and are used in biotechnology. This study shows that empty synthetic shells with different end-cap structures can be derived from a specific microcompartment, demonstrating the plasticity of BMC-based biomaterials. It also discovers new nanotube and nanocone morphologies that share architectural principles with other structures.
ADVANCED MATERIALS
(2023)
Article
Nanoscience & Nanotechnology
Jianhui Zhang, Vikramjeet Singh, Wei Huang, Priya Mandal, Manish K. Tiwari
Summary: We have developed liquid-repellent coatings with rapid self-healing and strong substrate adhesion by utilizing synergistic chemistry between polyurethane and hydrophobic metal-organic framework (MOF) nanoparticles. This nanocomposite features a nanohierarchical morphology and exhibits excellent liquid repellence. Through the incorporation of donor-acceptor self-assembly units, the polyurethane base polymer achieves high strength, excellent self-healing property, and strong adhesion strength on multiple substrates.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Polymer Science
Zhiliang Li, Duyen K. Tran, Mary Nguyen, Tengyue Jian, Feng Yan, Samson A. Jenekhe, Chun-Long Chen
Summary: This study presents the synthesis of a novel amphiphilic diblock peptoid with a terminal conjugated oligoaniline, which self-assembles into highly crystalline nanotubes with excellent stability and conductivity. The ordered structure directed by the peptoid allows for efficient electrical transport, showcasing a promising strategy for creating complex nanostructures with useful electronic and optoelectronic properties.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Zizhao Huang, Tao Jiang, Jie Wang, Xiang Ma, He Tian
Summary: This study monitored the self-assembly process of chiral DPAC derivatives in real time using vibration-induced emission, revealing distinct optical and morphological characteristics of different assemblies. Additionally, strong circularly polarized luminescence was induced during the morphology transformation process. The excited-state characteristics of the self-assemblies allowed effective investigation of the relationship between molecular aggregation and conformational change.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xiangyang Bai, Qingxue Sun, Hao Cui, Luis P. B. Guerzoni, Stefan Wuttke, Fabian Kiessling, Laura De Laporte, Twan Lammers, Yang Shi
Summary: Polymer self-assembly is a crucial process in materials engineering, but currently most methods are based on non-covalent bonding. In this study, a novel mechanism of covalent polymer self-assembly is discovered, addressing the drawbacks of non-covalent self-assembly. By tuning the covalent crosslinking rate, precise control over the size range of nanogels is achieved. This innovative assembly method has the potential to revolutionize multiscale materials fabrication in applications such as drug delivery and tissue engineering.
ADVANCED MATERIALS
(2022)
Article
Nanoscience & Nanotechnology
Guolong Gu, Chen Chen, Shichao Zhang, Bo Yin, Jianxin Wang
Summary: A novel strategy of delivering nitric oxide (NO) for cancer chemotherapy was proposed using prodrug dimer self-assembly nanoparticles of NO donors, which significantly improved drug loading and delivery efficiencies, ultimately inducing tumor cell apoptosis. This approach opened up a new avenue for cancer chemotherapy and laid a theoretical basis for clinical translation of NO-based gas chemotherapy.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Chantalle J. Krajewska, Alexander E. K. Kaplan, Matthias Kick, David B. Berkinsky, Hua Zhu, Tara Sverko, Troy Van Voorhis, Moungi G. Bawendi
Summary: Using different evaporation rates of the dispersion solvent, controlled assembly of CsPbBr3 nanoplatelets was achieved. Electron microscopy, X-ray scattering, and diffraction confirmed the superlattice structures in both the face-down and edge-up configurations. Polarization-resolved spectroscopy revealed significantly polarized emission in the edge-up superlattices compared to the face-down counterparts. Variable temperature X-ray diffraction revealed a uniaxial negative thermal expansion in ultrathin nanoplatelets, explaining the anomalous temperature dependence of the emission energy. Additional structural aspects were investigated by multilayer diffraction fitting, showing a decrease in superlattice order and an expansion of the organic sublattice and lead halide octahedral tilt with decreasing temperature.
Article
Engineering, Environmental
Chunling Hu, Lingshan Miao, Qian Yang, Xiaozhong Yu, Li Song, Yiyao Zheng, Chuanchuan Wang, Lei Li, Lianwen Zhu, Xuebo Cao, Helin Niu
Summary: This study successfully fabricated the NiCoO2@CNTs@NF integrated electrode with outstanding capacitive properties and stabilities by combining CNTs with NiCoO2 nanosheets. Furthermore, the ASCs based on this electrode exhibited high specific capacitance, excellent rate capability, durable stability, and high energy density.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Ramiro Quiros-Ovies, Maria Laborda, Natalia Martin Sabanes, Lucia Martin-Perez, Sara Moreno-Da Silva, Enrique Burzuri, Victor Sebastian, Emilio M. Perez, Jesus Santamaria
Summary: This article introduces a method for efficient exfoliation of MoS2 layers by utilizing its excellent MW absorption properties. The method involves rapid heating to induce near-instantaneous evaporation of a low boiling point solvent, leading to the separation of MoS2 layers with high efficiency. The method shows high yields, good quality, and large area coverage.
Article
Chemistry, Inorganic & Nuclear
Goncalo Valente, Maria Esteve-Rochina, Sergio P. C. Alves, Jose M. G. Martinho, Enrique Orti, Joaquin Calbo, Filipe A. Almeida Paz, Joao Rocha, Manuel Souto
Summary: This study presents an innovative synthesis method for producing highly crystalline and stable perylene-based coordination polymers. The materials have tunable optical and electrochemical properties, and exhibit high stability in the solid state.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Julia Villalva, Amalia Rapakousiou, Miguel A. Monclus, Juan Pedro Fernandez Blazquez, Jimena de la Vega, Alicia Naranjo, Mariano Vera-Hidalgo, Mariia Luisa Ruiz-Gonzalez, Henrik Pedersen, Emilio M. Perez
Summary: In order to address the poor individualization and interfacial adhesion in SWNT-polymer composites, this study investigates the use of a mechanical bond to wrap SWNTs with a layer of polymeric material. The resulting mechanically interlocked nanotubes (MINTs) show improved individualization and significantly increased mechanical properties compared to the matrix polymer. This strategy could be applied to produce SWNTs interlocked with polymer layers of various designs for polymer reinforcement.
Article
Chemistry, Multidisciplinary
Victor Garcia-Lopez, Niccolo Giaconi, Lorenzo Poggini, Joaquin Calbo, Amelie Juhin, Brunetto Cortigiani, Javier Herrero-Martin, Enrique Orti, Matteo Mannini, Miguel Clemente-Leon, Eugenio Coronado
Summary: The synthesis and characterization of a new Co(II) spin-crossover (SCO) complex based on a 4'-(4-carboxyphenyl)-2,2':6',2''-terpyridine ligand are described. The complex can be successfully grafted on the surface of silver while maintaining the spin-crossover behavior. Various techniques including AFM, MALDI-TOF MS, Raman spectroscopy, and XPS measurements confirmed the formation of a monolayer of intact molecules grafted onto the Ag surface through carboxylate groups. Raman spectroscopy, XPS, and XAS supported by first-principles calculations demonstrated a gradual spin transition of the deposited molecules with temperature, which is unprecedented for a monolayer of molecules directly grafted onto a metallic surface.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Arturo Oro, Fernando Romeo-Gella, Josefina Perles, Jesus M. Fernandez-Garcia, Ines Corral, Nazario Martin
Summary: The bottom-up synthesis of 3D tetrahedraphene, a molecular nanographene, is reported. The molecule exhibits a highly symmetric arrangement and shows aggregation induced fluorescence change in solution and precipitated solid.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sofia Mena-Hernando, Matthew Eaton, Juan P. Fernandez-Blazquez, Alejandro Lopez-Moreno, Henrik Pedersen, Emilio M. Perez
Summary: The study shows that derivatization of single-walled carbon nanotubes as mechanically interlocked derivatives (MINTs) is an effective strategy to optimize the interaction between SWNT fillers and the polymer matrix, leading to significant improvements in the mechanical properties of polymers.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Rafael Garcia-Meseguer, Enrique Orti, Inaki Tunon, J. Javier Ruiz-Pernia, Juan Arago
Summary: Polyethylene terephthalate (PET) is a commonly used polyester plastic in textiles and packaging, but it is also one of the most discarded after one use. The enzymatic biodegradation of PET has gained interest in recent years. The study investigated the molecular origin of the enhanced catalytic activity of FAST-PETase in PET degradation, finding that the rate-limiting reaction step for FAST-PETase is the acylation stage with a lower energy barrier compared to PETase. The enhancement is mainly attributed to the N233K mutation, inducing a chain folding that affects the catalytic triad and decreases the catalytic barrier.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Manuel A. Martinez, Daniel Aranda, Enrique Orti, Juan Arago, Luis Sanchez
Summary: The self-assembling features of amphiphilic N-annulated perylene bisimides (N-PBIs) 1-4 in water were investigated experimentally and theoretically. The hydrophilic/hydrophobic ratio, determined by the oligo(ethylene) glycol (OEG) chains in the monomers, plays a significant role in the enthalpy of self-assembly. Molecular dynamic simulations revealed the influence of the initial arrangement of hydrophilic side chains and water-side chain interactions on the enthalpy contribution and overall stability of the aggregated species in water.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Ivan Soriano-Diaz, Enrique Orti, Angelo Giussani
Summary: In this study, density functional theory calculations were used to investigate three cyclometallated Ir(III) complexes, [Ir(ppy)(2)(bpy)](+), [Ir(ppy)(2)(pbpy)](+), and [Ir(ppy)(2)(dpbpy)](+), in order to explain their different photophysical properties. Despite sharing the same molecular skeleton, the complexes exhibited different emission quantum yields, which was previously attributed to a different ability to non-radiatively decay through axial metal-centered triplet states. This study revealed a new non-radiative decay path mediated by equatorial metal-centered states, which better explained the observed photoemission properties.
DALTON TRANSACTIONS
(2023)
Article
Nanoscience & Nanotechnology
Felipe Viela, Ingrid V. Ortega, Jaime J. Hernandez, Isabel Rodriguez, Sara Moreno-Da Silva, Alejandro Lopez-Moreno, Emilio M. Perez, Cristina Flors
Summary: Mechanobactericidal nanomaterials are promising antimicrobial strategies that rely on mechanical interactions with bacteria and overcome antibiotic resistance. However, the detailed mechanisms behind the killing effects are not well understood. This study investigates the real-time response of bacteria to weak mechanical interactions with nanostructured topographies and nanodarts, shedding light on the complex mechanisms of mechanically induced bacterial death.
Article
Materials Science, Multidisciplinary
Mauricio Caicedo-Reina, Manuel Perez-Escribano, Javier Urieta-Mora, Ines Garcia-Benito, Joaquin Calbo, Alejandro Ortiz, Braulio Insuasty, Agustin Molina-Ontoria, Enrique Orti, Nazario Martin
Summary: A tailored design of asymmetric hole-transporting materials (HTMs) was reported using a family of new HTMs based on the use of the 5H-dithieno[3,2-b:2’,3’-d]pyran (DTP) moiety. The optoelectronic, electrochemical, and thermal properties of the new HTMs were experimentally and theoretically characterized, showing significant differences in the thermal behavior prompted by different alkyl chain lengths attached to the DTP core. The morphological behavior of the new HTMs played an important role in the deposition on the top surface of the perovskite layer in perovskite solar cells (PSCs).
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Sergio Ramirez-Barroso, Fernando Romeo-Gella, Jesus M. Fernandez-Garcia, Siyang Feng, Lara Martinez-Fernandez, David Garcia-Fresnadillo, Ines Corral, Nazario Martin, Reinhold Wannemacher
Summary: The intriguing photophysical properties of three curved nanographenes were investigated using time-resolved and temperature-dependent photoluminescence spectroscopy. The study found that CNG 7 and 8 exhibited dual fluorescence and phosphorescence at low temperature, as well as thermally activated delayed fluorescence in a narrow temperature range of 100-140 K.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Physical
Manuel Perez-Escribano, Alberto Fernandez-Alarcon, Enrique Orti, Juan Arago, Jesus Cerda, Joaquin Calbo
Summary: The design of hole-transporting materials (HTMs) as p-type semiconductors for (opto)electronics has received significant attention in recent years. However, the role of molecular shape, material morphology, and dynamic disorder in HTM charge transport has been overlooked. In this study, we characterize the charge transport properties of a novel HTM and compare it with a conventional HTM. Our theoretical calculations reveal the strong influence of molecular shape, dynamic structural fluctuations, and crystal morphology on the charge transport.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Multidisciplinary
Diego J. Vicent, Manuel Perez-Escribano, Abel Cardenas-Valdivia, Ana Barragan, Joaquin Calbo, Jose I. Urgel, David Ecija, Jose Santos, Juan Casado, Enrique Orti, Nazario Martin
Summary: This study focuses on the investigation of relatively unknown tetrabromo-p-quinodimethanes (TBQs) as molecular building blocks. Five derivatives incorporating tetrabromo-anthraquinodimethane (TBAQ) units are showcased, revealing their warped geometry and complex NMR pattern. The study also assesses the sublimation, self-assembly, and reactivity of TBQ3 on Au(111).
