Article
Chemistry, Multidisciplinary
Manuel A. Martinez, Elisa E. Greciano, Jorge Cuellar, Jose M. Valpuesta, Luis Sanchez
Summary: In this study, a highly emissive amphiphilic N-annulated PBI 1 decorated with oligo ethylene glycol (OEG) side chains was synthesized. Compound 1 self-assembles in water to form globular aggregates, demonstrating good solubility and stability in aqueous media. The UV-Vis spectra and solvent denaturation experiments provided insights into the self-assembly process and stability of compound 1 in different solvents.
Article
Chemistry, Physical
Huang Fang, Botond Tyukodi, W. Benjamin Rogers, Michael F. Hagan
Summary: In contrast to most self-assembling synthetic materials, biological self-assembly processes are self-limited. This article studies a class of self-closing assemblies: cylindrical tubules assembled from triangular monomers. By controlling the preferred curvature of the monomers and their interaction strengths, different size scales can be targeted in the assembly process.
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, 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
Engineering, Electrical & Electronic
Vinod Kumar Vishwakarma, Mrinmoy Roy, Rajan Singh, Doddamane Sreenivasamurthy Shankar Rao, Roy Paily, Achalkumar Ammathnadu Sudhakar
Summary: Researchers designed and synthesized four imidazole-containing liquid-crystalline compounds based on naphthalene and perylene bisimide. These compounds possessed liquid crystallinity and solution processability, making them suitable for use as organic semiconductors. The compounds exhibited different columnar phases, with greater thermal stability and lower band gaps observed in both naphthalene and perylene bisimide derivatives. Two of the compounds were used for the fabrication of organic field-effect transistors, demonstrating high hole mobility in normal air conditions.
ACS APPLIED ELECTRONIC MATERIALS
(2023)
Article
Engineering, Electrical & Electronic
Vinod Kumar Vishwakarma, Mrinmoy Roy, Rajan Singh, Doddamane Sreenivasamurthy Shankar Rao, Roy Paily, Achalkumar Ammathnadu Sudhakar
Summary: We designed and synthesized four liquid-crystalline derivatives based on naphthalene and perylene bisimide with imidazole-containing groups. These compounds with 10 flexible peripheral chains possess liquid crystallinity and solution processability, suitable for use as organic semiconductors. They showed different columnar phases and exhibited higher thermal stability and lower band gaps. The NI derivatives showed larger Stokes shifts, while the PI derivatives exhibited very high molar extinction coefficients. Two solution-processable liquid-crystalline compounds (NI-12 and PI-12) were used to fabricate organic field-effect transistors, with NI-12 derivatives showing a hole mobility of 1.99 cm2/V center dot s and PI-12 derivatives showing a hole mobility of 0.63 cm2/V center dot s at room temperature in normal air conditions.
ACS APPLIED ELECTRONIC MATERIALS
(2023)
Article
Chemistry, Analytical
Wei Zhou, Jiaze Hou, Yongxin Li, Huipeng Zhou, Hui Huang, Ling Zhang, Muhammad Azhar Hayat Nawaz, Cong Yu
Summary: A novel fluorescence detection method based on a perylene probe was developed for highly efficient discrimination of multiple proteins, utilizing single-stranded DNA to induce probe aggregation. A sensor array was designed to successfully discriminate nine representative proteins with 100% accuracy of cross validation, demonstrating differentiation irrespective of protein concentration.
Article
Chemistry, Multidisciplinary
Rong Sheng Li, Jiahui Liu, Hu Shi, Ping Ping Hu, Yao Wang, Peng Fei Gao, Jian Wang, Moye Jia, Hongwei Li, Yuan Fang Li, Chengde Mao, Na Li, Cheng Zhi Huang
Summary: Golgi apparatus-targeted nano-mechanical disruption is an attractive approach for killing cancer cells by multimodal mechanism and avoiding drug resistance. The transformable peptide C6RVRRF4KY can self-assemble into nontoxic nanoparticles in aqueous medium but transformed into left-handed helical fibrils (L-HFs) after targeting and furin cleavage in the Golgi apparatus of cancer cells, leading to mechanical disruption and death of cancer cells without acquired drug resistance. This nanomechanical disruption concept should also be applicable to multidrug-resistant bacteria and viruses.
Article
Chemistry, Multidisciplinary
Joonsik Seo, Mohammed Iqbal Khazi, Kwangmin Bae, Jong-Man Kim
Summary: Self-assembly is an efficient method for designing functional nanomaterials. In this study, a functional perylene diimide (PDI) derivative, PDI-DA, was designed to investigate the pathway complexity during self-assembly. The temperature control and UV-induced polymerization helped capture the intermediates and understand the mechanism. The morphological evolution showed two kinetic intermediates before transforming into the thermodynamic product, and spectroscopic studies revealed distinct H- and J-aggregates for kinetic and thermodynamic products respectively. The polymerized PDI-DA exhibited reversible switching between J- and H-aggregates.
Review
Chemistry, Multidisciplinary
Nadjib Kihal, Ali Nazemi, Steve Bourgault
Summary: Research has shown that supramolecular bio-assemblies based on PDI have unique structures and functionalities. By conjugating PDI derivatives with biological molecules, nanoassemblies with tailored functional properties can be constructed.
Article
Chemistry, Multidisciplinary
Pan-Pan Sun, Bao-Liang Han, Hong-Guang Li, Cheng-Kai Zhang, Xia Xin, Jian-Min Dou, Zhi-Yong Gao, Di Sun
Summary: This study systematically investigates the complex dynamics of a Cu-I nanocluster, Cu8a, and deduces the directed self-assembly process by monitoring the aggregation-induced emission and electron microscopy. The polymorphism and different emission properties of Cu NCs aggregates are successfully captured, and the structure-optical property relationship is established. Furthermore, the introduction of carbon dots as luminescent agents enriches the visualization fluorescence window, offering great potential for real-time optical sensing of materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Li Zhang, Li Yang, Yining He, Ji-Min Han
Summary: A helical humidity-resistive sensor was fabricated using solution processing, which showed high response and fast response and recovery time due to the supramolecular self-assembly mechanism and the reaction of viologen with water.
JOURNAL OF MATERIALS CHEMISTRY A
(2022)
Article
Chemistry, Multidisciplinary
Qiumeng Chen, Yahui Li, Ming Liu, Xuan Wu, Jianliang Shen, Liangliang Shen
Summary: A new strategy for constructing helical nanowires via polymerization-induced self-assembly (PISA) mediated by a fluorinated stabilizer block has been developed in this work. Ultralong nanowires with helical structure can be readily produced in a wide range of block compositions. The generality of this strategy was well testified by expanding monomer types, showing a morphology transition from spheres to helical nanowires during aging of achiral BCP nano-objects.
Article
Nanoscience & Nanotechnology
Yuchuan Xiao, Jiayu Tao, Xuan Peng, Yuting Song, Peng Lei, Haijun Xu, Xunwen Xiao, Bin Tu, Qingdao Zeng
Summary: The structures of 2D self-assembled molecular networks formed by PBI derivatives with different functional groups were investigated, revealing different growth patterns depending on the substituents introduced. In particular, PBI with amide groups showed potential in forming a 2D porous molecular network through hierarchy self-assembly. The structure of the network could be adjusted by changing the concentration, as confirmed by density functional theory calculations.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Yi Wang, Jun Chen, Chenhui Zhu, Baixu Zhu, Soojin Jeong, Yi Yi, Yang Liu, Joshua Fiadorwu, Peng He, Xingchen Ye
Summary: Polymer-inorganic nanocomposites based on polymer-grafted nanocrystals (PGNCs) are being used in technologically relevant applications due to their unique physical, chemical, and mechanical properties. This study demonstrates a kinetically controlled assembly of binary superstructures from a homogeneous disordered PGNC mixture using solvent vapor annealing (SVA), providing insight into the multistep crystallization pathway of PGNCs. By varying the solvent vapor pressure during SVA, exquisite control of the rate and extent of PGNC assembly is achieved, allowing for the synthesis of multicomponent PGNC superstructures with multifunctionalities and emergent properties.
Article
Polymer Science
Shu-Gui Yang, Liang-Qing Zhang, Jiaming Cui, Xiang-bing Zeng, Baolin Guo, Feng Liu, Goran Ungar
Summary: This study used two-photon confocal laser microscopy to obtain three-dimensional images of the morphology of poly(lactic acid) after shear-induced crystallization. By doping the polymer with Nile Red, the necessary fluorescence contrast was achieved. The results showed that the shape of the resulting cylindrites, or large-diameter shish-kebabs, was influenced by the shear method used. Additionally, the formation of a row of spherulites was observed during fiber pull, which was attributed to crystallization-induced volume contraction.
Article
Polymer Science
Yanlin Shi, Sung-Po R. Chen, George Fragkiadakis, Daniele Parisi, Virgil Percec, Dimitris Vlassopoulos, Michael J. Monteiro
Summary: The shape, breadth, and average molecular weight of the overall molecular weight distribution (MWD) are important for determining polymer properties. Traditional methods can only achieve desired Gaussian distribution through complex modeling, while living radical polymerization provides a simpler route. Blending low-reactive RAFT agents allows the construction of square, slanted, and chair-like MWDs, providing control over MWD shape and breadth. This blending method overcomes difficulties in producing unusual MWDs and offers a general synthetic strategy for studying structure-property relationships of polymers.
Article
Polymer Science
Devendra S. Maurya, Jasper Adamson, Nabil Bensabeh, Gerard Lligadas, Virgil Percec
Summary: DMSO is an interesting solvent for copper-catalyzed living radical polymerization due to its ability to provide high conversion and absence of termination. Although it is not the most efficient solvent for disproportionation of Cu(I)X, DMSO allows for the development of complex-architecture methodologies by living and immortal polymerizations. The mechanism behind this precision is currently being investigated.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Physical
Kazuma Hamaguchi, Huanjun Lu, Shota Okamura, Satoshi Kajiyama, Junya Uchida, Shunsuke Sato, Go Watanabe, Yoshiki Ishii, Hitoshi Washizu, Goran Ungar, Takashi Kato
Article
Polymer Science
Jack F. Douglas, Vivek M. Prabhu, Yuanchi Ma, Steven D. Hudson, Paul F. Salipante
Summary: In this study, we examine whether the mode-coupling theory of 1-56; Ferrell, R. A. Decoupled-Mode Dynamical Scaling Theory of the 1172] can accurately describe the dynamic structure factor of near-critical polyelectrolyte complex (PC) solutions through dynamic light scattering (DLS) measurements. The results show that there is good qualitative agreement between the DLS measurements and the KF theory, indicating that the KF theory can robustly describe collective diffusion in these complex charged polyelectrolyte blends under near-critical conditions.
Article
Polymer Science
Virgil Percec, Dipankar Sahoo, Jasper Adamson
Summary: This article organized for the first time the stimuli-responsive principles of supramolecular organizations emerging from self-assembling and self-organizable dendrons, dendrimers, and dendronized polymers, which is fundamental to natural and life sciences.
Article
Polymer Science
Adrian Moreno, Gerard Lligadas, Jasper Adamson, Devendra S. Maurya, Virgil Percec
Summary: The Nobel Prize in Chemistry for 2022 was awarded to Bertozzi, Meldal, and Sharpless for their contribution to the development of click chemistry and biorthogonal chemistry. Since 2001, when click chemistry was proposed by Sharpless's laboratory, synthetic chemists have favored click reactions as a preferred method to create new functions. This perspective summarizes the research conducted in our laboratories on CuAAC, TBC, and TERMINI click reactions, and their applications in assembling complex macromolecules and self-organizations with biological relevance.
Article
Pharmacology & Pharmacy
Juncheng Lu, Elena N. Atochina-Vasserman, Devendra S. Maurya, Muhammad Irhash Shalihin, Dapeng Zhang, Srijay S. Chenna, Jasper Adamson, Matthew Liu, Habib Ur Rehman Shah, Honey Shah, Qi Xiao, Bryn Queeley, Nathan A. Ona, Erin K. Reagan, Houping Ni, Dipankar Sahoo, Mihai Peterca, Drew Weissman, Virgil Percec
Summary: The use of viral and synthetic vectors for nucleic acid delivery is crucial for the rapid development of effective COVID-19 vaccines. Lipid nanoparticles (LNPs) composed of phospholipids, PEG-conjugated lipids, cholesterol, and ionizable lipids have been employed as the leading nonviral delivery vector for COVID-19 mRNA vaccines by BioNTech/Pfizer and Moderna. In this study, a methodology involving screening libraries was used to discover the molecular design principles necessary for targeted mRNA delivery to specific organs, using a one-component ionizable multifunctional amphiphilic Janus dendrimer (IAJD) derived from plant phenolic acids. These design principles simplify the synthesis of IAJDs and the assembly of monodisperse dendrimersome nanoparticles (DNPs) with predictable dimensions, ultimately enhancing accessibility to diverse mRNA-based vaccines and nanotherapeutics.
Article
Chemistry, Multidisciplinary
Dipankar Sahoo, Emad Aqad, Mihai Peterca, Virgil Percec
Summary: This publication reports the structural analysis of the 3D self-organizations of HATn molecules, revealing the formation of highly ordered helical and nonhelical pyramidal and discotic columns. It demonstrates that a single building block can self-organize into different assemblies via its constitutional isomers. The findings raise important questions about the current understanding of helical self-organizations.
Article
Chemistry, Multidisciplinary
Dipankar Sahoo, Emad Aqad, Mihai Peterca, Virgil Percec
Summary: The molecular structures of 3D crystal and 2D liquid crystal phases of discotic molecules have never been determined at the molecular level. This study investigates the molecular structure of HATn self-organizations and presents the molecular structures of HAT4 in its crystal and liquid crystal states.
Article
Chemistry, Multidisciplinary
Ningdong Huang, Weiheng Huang, Zhenlin Luo, Wangsheng Chu, Goran Ungar
Summary: 3D crystalline order with 1 nm resolution is observed in aqueous solutions of supramolecular nanotubes containing 94% water, at concentrations as low as 6 wt%. The nanotubes are formed by supramolecular rings of star-like organic ions, which stack on top of each other to form long hollow tubes with 15 nm outer diameter. The high 3D order is attributed to long-range attraction between like-charged tubes and amplified charge modulation by the extremely high intra-tube correlation length.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Polymer Science
Shu-Gui Yang, Liang-Qing Zhang, Changlong Chen, Jiaming Cui, Xiang-bing Zeng, Liying Liu, Feng Liu, Goran Ungar
Summary: Polymorphism of semicrystalline polymers has a significant impact on their physical properties, but determining the shape, spatial distribution, and volume fraction of different coexisting crystal polymorphs remains a challenge. In this study, 3D imaging using two-photon fluorescence confocal microscopy and synchrotron X-ray beam scanning was employed to visualize and quantify the different crystal forms and their specific morphologies. The ability to distinguish crystal forms and their distributions is demonstrated, providing valuable insights into the processing and properties of semicrystalline polymers.