共查询到20条相似文献,搜索用时 11 毫秒
1.
Dr. Luka Đorđević Dr. Hiroaki Sai Dr. Yang Yang Dr. Nicholas A. Sather Dr. Liam C. Palmer Prof. Dr. Samuel I. Stupp 《Angewandte Chemie (International ed. in English)》2023,62(17):e202214997
Supramolecular polymerization of π-conjugated amphiphiles in water is an attractive approach to create functional nanostructures. Here, we report on the synthesis, optoelectronic and electrochemical properties, aqueous supramolecular polymerization, and conductivity of polycyclic aromatic dicarboximide amphiphiles. The chemical structure of the model perylene monoimide amphiphile was modified with heterocycles, essentially substituting one fused benzene ring with thiophene, pyridine or pyrrole rings. All the heterocycle-containing monomers investigated underwent supramolecular polymerization in water. Large changes to the monomeric molecular dipole moments led to nanostructures with low electrical conductivity due to diminished interactions. Although the substitution of benzene with thiophene did not notably change the monomer dipole moment, it led to crystalline nanoribbons with 20-fold higher electrical conductivity, due to enhanced dispersion interactions as a result of the presence of sulfur atoms. 相似文献
2.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(50):16224-16228
The self‐assembly of a new perylene bisimide (PBI) organogelator with 1,7‐dimethoxy substituents in the bay position affords non‐fluorescent H‐aggregates at high cooling rates and fluorescent J‐aggregates at low cooling rates. Under properly adjusted conditions, the kinetically trapped “off‐pathway” H‐aggregates are transformed into the thermodynamically favored J‐aggregates, a process that can be accelerated by the addition of J‐aggregate seeds. Spectroscopic studies revealed a subtle interplay of π–π interactions and intra‐ and intermolecular hydrogen bonding for monomeric, H‐, and J‐aggregated PBIs. Multiple polymerization cycles initiated from the seed termini demonstrate the living character of this chain‐growth supramolecular polymerization process. 相似文献
3.
Yike Yao Dr. Liang Gao Prof. Dr. Chunhua Cai Prof. Dr. Jiaping Lin Prof. Dr. Shaoliang Lin 《Angewandte Chemie (International ed. in English)》2023,62(9):e202216872
Introducing a second component is an effective way to manipulate polymerization behavior. However, this phenomenon has rarely been observed in colloidal systems, such as polymeric nanoparticles. Here, we report the supramolecular polymerization of polymeric nanorods mediated by block copolymers. Experimental observations and simulation results illustrate that block copolymers surround the polymeric nanorods and mainly concentrate around the two ends, leaving the hydrophobic side regions exposed. These polymeric nanorods connect in a side-by-side manner through hydrophobic interactions to form bundles. As polymerization progresses, the block copolymers gradually deposit onto the bundles and finally assemble into helical nanopatterns on the outermost surface, which terminates the polymerization. It is anticipated that this work could offer inspiration for a general strategy of controllable supramolecular polymerization. 相似文献
4.
Prof. Zhijian Chen Yong Liu Wolfgang Wagner Dr. Vladimir Stepanenko Dr. Xiangkui Ren Dr. Soichiro Ogi Prof. Frank Würthner 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(21):5823-5827
A new amphiphilic BF2-azadipyrromethene (aza-BODIPY) dye 1 has been synthesized using a CuI-catalyzed “click” reaction. For this dye, two self-assembly pathways that lead to different type of J-aggregates with distinct near-infrared optical properties have been discovered. The metastable off-pathway product displays a broad, structureless absorption band while the thermodynamically stable on-pathway aggregate exhibits the characteristic spectral features of a J-aggregate, that is, red-shifted intense absorption band with significantly narrowed linewidth. The morphology and structure of the aggregates were studied by atomic force microscopy, transmission and scanning electron microscopy. The aggregation processes of 1 were investigated by temperature- and concentration-dependent UV/Vis spectroscopy and evaluated by models for cooperative self-assembly. 相似文献
5.
Hucheng Wang Dr. Xiaoming Fu Guanyao Gu Shengyu Bai Dr. Runlai Li Prof. Weimin Zhong Prof. Xuhong Guo Dr. Rienk Eelkema Prof. Jan H. van Esch Prof. Zhixing Cao Prof. Yiming Wang 《Angewandte Chemie (International ed. in English)》2023,62(43):e202310162
Living organisms are capable of dynamically changing their structures for adaptive functions through sophisticated reaction-diffusion processes. Here we show how active supramolecular hydrogels with programmable lifetimes and macroscopic structures can be created by relying on a simple reaction-diffusion strategy. Two hydrogel precursors (poly(acrylic acid) PAA/CaCl2 and Na2CO3) diffuse from different locations and generate amorphous calcium carbonate (ACC) nanoparticles at the diffusional fronts, leading to the formation of hydrogel structures driven by electrostatic interactions between PAA and ACC nanoparticles. Interestingly, the formed hydrogels are capable of autonomously disintegrating over time because of a delayed influx of electrostatic-interaction inhibitors (NaCl). The hydrogel growth process is well explained by a reaction-diffusion model which offers a theoretical means to program the dynamic growth of structured hydrogels. Furthermore, we demonstrate a conceptual access to dynamic information storage in soft materials using the developed reaction-diffusion strategy. This work may serve as a starting point for the development of life-like materials with adaptive structures and functionalities. 相似文献
6.
Maithreyi Ramakrishnan Alexander van Teijlingen Tell Tuttle R. V. Ulijn 《Angewandte Chemie (International ed. in English)》2023,62(18):e202218067
Interest in peptide-based supramolecular materials has grown extensively since the 1980s and the application of computational methods has paralleled this. These methods contribute to the understanding of experimental observations based on interactions and inform the design of new supramolecular systems. They are also used to virtually screen and navigate these very large design spaces. Increasingly, the use of artificial intelligence is employed to screen far more candidates than traditional methods. Based on a brief history of computational and experimentally integrated investigations of peptide structures, we explore recent impactful examples of computationally driven investigation into peptide self-assembly, focusing on recent advances in methodology development. It is clear that the integration between experiment and computation to understand and design new systems is becoming near seamless in this growing field. 相似文献
7.
Zhenwen Wang Dr. Lei Mei Dr. Chenxing Guo Song Huang Prof. Dr. Wei-Qun Shi Dr. Xiaowei Li Wen Feng Prof. Xiaopeng Li Prof. Dr. Cheng Yang Prof. Lihua Yuan 《Angewandte Chemie (International ed. in English)》2023,62(14):e202216690
Use of abiotic chemical systems for understanding higher order superstructures is challenging. Here we report a ring-in-ring(s) system comprising a hydrogen-bonded macrocycle and cyclobis(paraquat-o-phenylene) tetracation ( o -Box ) or cyclobis(paraquat-p-phenylene) tetracation ( CBPQT 4+, p -Box ) that assembles to construct discrete higher order structures with adaptive conformation. As indicated by mass spectrometry, computational modeling, NMR spectroscopy, and single-crystal X-ray diffraction analysis, this ring-in-ring(s) system features the box-directed aggregation of multiple macrocycles, leading to generation of several stable species such as H4G ( 1 a / o -Box ) and H5G ( 1 a / o -Box ). Remarkably, a dimeric shish-kebab-like ring-in-rings superstructure H7G2 ( 1 a / o -Box ) or H8G2 ( 1 a / p -Box ) is formed from the coaxial stacking of two ring-in-rings units. The formation of such unique dimeric superstructures is attributed to the large π-surface of this 2D planar macrocycle and the conformational variation of both host and guest. 相似文献
8.
Dr. Catriona C. James Prof. Dr. Bas de Bruin Prof. Dr. Joost N. H. Reek 《Angewandte Chemie (International ed. in English)》2023,62(41):e202306645
The importance of transition metal catalysis is exemplified by its wide range of applications, for example in the synthesis of chemicals, natural products, and pharmaceuticals. However, one relatively new application is for carrying out new-to-nature reactions inside living cells. The complex environment of a living cell is not welcoming to transition metal catalysts, as a diverse range of biological components have the potential to inhibit or deactivate the catalyst. Here we review the current progress in the field of transition metal catalysis, and evaluation of catalysis efficiency in living cells and under biological (relevant) conditions. Catalyst poisoning is a ubiquitous problem in this field, and we propose that future research into the development of physical and kinetic protection strategies may provide a route to improve the reactivity of catalysts in cells. 相似文献
9.
Dr. Mitsuaki Yamauchi Kanako Nakatsukasa Naoki Kubo Prof. Dr. Hiroko Yamada Prof. Dr. Sadahiro Masuo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(1):e202314329
Colloidal quantum dots (QDs) exhibit important photophysical properties, such as long-range energy diffusion, miniband formation, and collective photoluminescence, when aggregated into well-defined superstructures, such as three-dimensional (3D) and two-dimensional (2D) superlattices. However, the construction of one-dimensional (1D) QD superstructures, which have a simpler arrangement, is challenging; therefore, the photophysical properties of 1D-arranged QDs have not been studied previously. Herein, we report a versatile strategy to obtain 1D-arranged QDs using a supramolecular polymer (SP) template. The SP is composed of self-assembling cholesterol derivatives containing two amide groups for hydrogen bonding and a carboxyl group as an adhesion moiety on the QDs. Upon mixing the SP and dispersed QDs in low-polarity solvents, the QDs self-adhered to the SP and self-arranged into 1D superstructures through van der Waals interactions between the surface organic ligands of the QDs, as confirmed by transmission electron microscopy. Furthermore, we revealed efficient photoinduced fluorescence resonance energy transfer between the 1D-arranged QDs by an in-depth analysis of the emission spectra and decay curves. 相似文献
10.
11.
Houchen Wang Yongjie Zhang Yuanfang Chen Hongfei Pan Prof. Dr. Xiangkui Ren Prof. Dr. Zhijian Chen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(13):5223-5230
An aza-BODIPY dye 1 bearing two hydrophobic fan-shaped tridodecyloxybenzamide pendants through 1,2,3-triazole linkages was synthesized by a click reaction and characterized. 1H NMR studies indicated that dye 1 exhibited variable conformations through intramolecular H-bonding interaction, which is beneficial for the polymorphism of aggregation. The thermodynamic, structural, and kinetic aspect of the supramolecular polymerization of dye 1 was investigated by UV/Vis absorption spectroscopy, IR spectroscopy, AFM, TEM, and SEM. Biphasic aggregation pathways of dye 1 , leads to the formation of off-pathway, metastable Agg. I and thermodynamically stable Agg. II with distinct H-aggregation spectra and nanoscale morphology. The living manner of the supramolecular polymerization of dye 1 was demonstrated in seeded polymerization experiments with temperature-modulated successive cooling–heating cycles. 相似文献
12.
Dr. Beatriz Matarranz Dr. Sandra Díaz-Cabrera Dr. Goutam Ghosh Dr. Israel Carreira-Barral Dr. Bartolome Soberats Prof. Dr. María García-Valverde Prof. Dr. Roberto Quesada Prof. Dr. Gustavo Fernández 《Angewandte Chemie (International ed. in English)》2023,62(17):e202218555
After more than three decades of extensive investigations on supramolecular polymers, strategies for self-limiting growth still remain challenging. Herein, we exploit a new V-shaped monomer design to achieve anticooperatively formed oligomers with superior robustness and high luminescence. In toluene, the monomer-oligomer equilibrium is shifted to the monomer side, enabling the elucidation of the molecular packing modes and the resulting (weak) anticooperativity. Steric effects associated with an antiparallel staircase organization of the dyes are proposed to outcompete aromatic and unconventional B−F⋅⋅⋅H−N/C interactions, restricting the growth at the stage of oligomers. In methylcyclohexane (MCH), the packing modes and the anticooperativity are preserved; however, pronounced solvophobic and chain-enwrapping effects lead to thermally ultrastable oligomers. Our results shed light on understanding anticooperative effects and restricted growth in self-assembly. 相似文献
13.
Muhammad Ghufran Rafique Dr. Jacob M. Remington Finley Clark Haochen Bai Dr. Violeta Toader Prof. Dmytro F. Perepichka Prof. Jianing Li Prof. Hanadi F. Sleiman 《Angewandte Chemie (International ed. in English)》2023,62(24):e202217814
Two-dimensional (2D) assemblies of water-soluble block copolymers have been limited by a dearth of systematic studies that relate polymer structure to pathway mechanism and supramolecular morphology. Here, we employ sequence-defined triblock DNA amphiphiles for the supramolecular polymerization of free-standing DNA nanosheets in water. Our systematic modulation of amphiphile sequence shows the alkyl chain core forming a cell membrane-like structure and the distal π-stacking chromophore block folding back to interact with the hydrophilic DNA block on the nanosheet surface. This interaction is crucial to sheet formation, marked by a chiral “signature”, and sensitive to DNA sequence, where nanosheets form with a mixed sequence, but not with a homogeneous poly(thymine) sequence. This work opens the possibility of forming well-ordered, bilayer-like assemblies using a single DNA amphiphile for applications in cell sensing, nucleic acid therapeutic delivery and enzyme arrays. 相似文献
14.
Dr. Fabian Schmidt Dr. Saner Poplata Dr. Danny Morris Dr. Stefan Burger M.Sc. Markus Hegelmann Prof. Dr. Jason B. Love Dr. Mirza Cokoja 《ChemCatChem》2024,16(6):e202301482
The development of inexpensive and effective catalysts for the epoxidation of olefins to epoxides, which are key commodities for the chemical industry, is a continuing challenge. In this context, we present a supramolecular solution with the development of new host-guest assemblies of sulfate ions and amidoammonium receptor cations that, for the first time, are shown to act as catalysts for olefin epoxidation by hydrogen peroxide under biphasic conditions. Analysis of the reaction mechanism shows that the reactive and oxidizing peroxymonosulfate is formed in the organic phase. Furthermore, a variety of readily available precursors may be used to form the supramolecular ion pairs (SIPs), which is enabling a large-scale synthesis of the catalysts while maintaining catalytic control and effectiveness. 相似文献
15.
Jean-Pierre Dutasta Brigitte Bibal Jean-Paul Declercq Beatrice Dubessy Jean-Christophe Mulatier Bernard Tinant 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1485-1488
The recent results in the chemistry of cavitands have proved that they are very efficient molecular receptors and potential precursors of molecular devices. In this context, we have investigated the synthesis and binding properties of phosphorylated cavitands. The stereoselective synthesis and the structural studies of the new compounds showed that these bowl-shaped molecules possess a well defined aromatic cavity surrounded by four phosphoryl groups (P=O or P=S). They are very efficient ligands for metal and organic cations. They are able to encapsulate cationic species by cooperative effect of the preorganized aromatic cavity and the four phosphorylated groups. Moreover, the upper and lower rim functionalitics can lead to the formation of molecular capsules and supramolecular assemblies whose properties and structures have been investigated by X-ray diffraction and NMR studies in solution. 相似文献
16.
Dr. Hong-Yu Lin Le-Yong Zhou Fang Mei Dr. Wei-Tao Dou Dr. Lianrui Hu Prof. Dr. Hai-Bo Yang Prof. Dr. Lin Xu 《Angewandte Chemie (International ed. in English)》2023,62(27):e202301900
Developing a new strategy to improve the self-assembly efficiency of functional assemblies in a confined space and construct hybrid functional materials is a significant and fascinating endeavor. Herein, we present a highly efficient strategy for achieving the supramolecular self-assembly of well-defined metallacages in microdroplets through continuous-flow microfluidic devices. The high efficiency and versatility of this approach are demonstrated by the generation of five representative metallacages in different solvents containing water, DMF, acetonitrile, and methanol in a few minutes with nearly quantitative yields, in contrast to the yields obtained with the hour-scale reaction time in a batch reactor. A ring-opening catalytic reaction of the metallacages was selected as a model reaction for exploring supramolecular catalysis in microdroplets, whereby the catalytic yield was enhanced by 2.22-fold compared to that of the same reaction in the batch reactor. This work illustrates a new promising approach for the self-assembly of supramolecular systems. 相似文献
17.
Dr. Irene Regeni Rituparno Chowdhury Kai Terlinden Dr. Shinnosuke Horiuchi Dr. Julian J. Holstein Dr. Sascha Feldmann Prof. Dr. Guido H. Clever 《Angewandte Chemie (International ed. in English)》2023,62(40):e202308288
A strategy to engineer the stacking of diketopyrrolopyrrole (DPP) dyes based on non-statistical metallosupramolecular self-assembly is introduced. For this, the DPP backbone is equipped with nitrogen-based donors that allow for different discrete assemblies to be formed upon the addition of Pd(II), distinguished by the number of π-stacked chromophores. A Pd3L6 three-ring, a heteroleptic Pd2L2L′2 ravel composed of two crossing DPPs (flanked by two carbazoles), and two unprecedented self-penetrated motifs (a Pd2L3 triple and a Pd2L4 quadruple stack), were obtained and systematically investigated. With increasing counts of stacked chromophores, UV/Vis absorptions red-shift and emission intensities decrease, except for compound Pd2L2L′2, which stands out with an exceptional photoluminescence quantum yield of 51 %. This is extraordinary for open-shell metal containing assemblies and explainable by an intra-assembly FRET process. The modular design and synthesis of soluble multi-chromophore building blocks offers the potential for the preparation of nanodevices and materials with applications in sensing, photo-redox catalysis and optics. 相似文献
18.
There is substantial recent interest worldwide in the construction of multiporphyrin assemblies which can either mimic naturally occurring multichromophore aggregates, such as the photosynthetic reaction center and the light harvesting complex of purple bacteria, or which can be used as electron- and/or energy-transfer molecular devices for advanced technological tasks. The metal-mediated self-assembly approach, which exploits the formation of coordination bonds between peripheral basic site(s) on the porphyrins and metal centers, has recently allowed the design and preparation of sophisticated supramolecular architectures whose complexity and function begin to approach the properties of naturally occurring systems. Within this framework, meso -pyridyl/phenyl porphyrins (PyPs), or strictly related chromophores, can provide geometrically well-defined connections to as many as four metal centers by coordination of the pyridyl groups. Several discrete assemblies of various nuclearities, in which the pyridylporphyrins are linkers binding metalloporphyrins and/or coordination compounds, have been constructed in recent years. Our contribution to this field is reviewed, with the aim of providing insight into the design of new, more elaborated architectures of higher order. 相似文献
19.
Jeong Sang Oh Dr. Ka Young Kim Minhye Kim Sukyoung Kim Prof. Sung Ho Jung Prof. Jong Hwa Jung 《Angewandte Chemie (International ed. in English)》2023,62(25):e202300913
We report the unique synthesis of chiral supramolecular tri- and penta-BCPs with controllable chirality using kinetically adjusted seeded supramolecular copolymerization in THF and DMSO (99 : 1, v/v). Tetraphenylethylene (d - and l -TPE) derivatives bearing d - and l -alanine side chains formed thermodynamically favored chiral products via a kinetically trapped in monomeric state with a long lag phase. In contrast, achiral TPE-G containing glycine moieties did not form a supramolecular polymer owing to the energy barrier in its kinetically trapped state. We show that the copolymerization of the metastable states of TPE-G not only enables the generation of supramolecular BCPs by the seeded living growth method, but also transfers chirality at the seed ends. This research demonstrates the generation of chiral supramolecular tri- and penta-BCPs with B-A-B, A-B-A-B-A, and C-B-A-B-C block patterns accompanying chirality transfer via seeded living polymerization. 相似文献
20.
Angshuman Das Saikat Ghosh Prof. Dr. Subi J. George 《Angewandte Chemie (International ed. in English)》2023,62(38):e202308281
Efficient circularly polarized luminescence (CPL) from purely organic molecules holds great promise for applications in displays, sensing, and bioimaging. However, achieving high dissymmetry values (glum) from organic chromophores remains a significant challenge. Herein, we present a bioinspired approach using adenosine triphosphate (ATP)-triggered supramolecular polymerization of a naphthalene diimide-derived monomer ( ANSG ) to induce CPL with a remarkable glum value of 1.1×10−2. The ANSG molecules undergo a templated, chiral self-assembly through a cooperative growth mechanism in the presence of ATP, resulting in scrolled nanotubes with aggregation-induced enhanced emission (AIEE) and induced CPL. Furthermore, we demonstrate the concept of chiroptical amplification of induced CPL by efficiently amplifying asymmetry using a mixture of chiral ATP and achiral pyrophosphate. This innovative approach opens numerous opportunities in the emerging field of circularly polarized luminescence. 相似文献