Understanding and controlling multicomponent co‐assembly is of primary importance in different fields, such as materials fabrication, pharmaceutical polymorphism, and supramolecular polymerization, but these aspects have been a long‐standing challenge. Herein, we discover that liquid–liquid phase separation (LLPS) into ion‐cluster‐rich and ion‐cluster‐poor liquid phases is the first step prior to co‐assembly nucleation based on a model system of water‐soluble porphyrin and ionic liquids. The LLPS‐formed droplets serve as the nucleation precursors, which determine the resulting structures and properties of co‐assemblies. Co‐assembly polymorphism and tunable supramolecular phase transition behaviors can be achieved by regulating the intermolecular interactions at the LLPS stage. These findings elucidate the key role of LLPS in multicomponent co‐assembly evolution and enable it to be an effective strategy to control co‐assembly polymorphism as well as supramolecular phase transitions.
In diverse biological systems, the oxidation of tyrosine to melanin or dityrosine is crucial for the formation of crosslinked proteins and thus for the realization of their structural, biological, and photoactive functionalities; however, the predominant factor in determining the pathways of this chemical evolution has not been revealed. Herein, we demonstrate for tyrosine‐containing amino acid derivatives, peptides, and proteins that the selective oxidation of tyrosine to produce melanin or dityrosine can be readily realized by manipulating the oxygen concentration in the reaction system. This oxygen‐dependent pathway selection reflects the selective chemical evolution of tyrosine to dityrosine and melanin in anaerobic and aerobic microorganisms, respectively. The resulting melanin‐ and dityrosine‐containing nanomaterials reproduce key functions of their natural counterparts with respect to their photothermal and photoluminescent characteristics, respectively. This work reveals the plausible role of oxygen in the chemical evolution of tyrosine derivatives and provides a versatile strategy for the rational design of tyrosine‐based multifunctional biomaterials.
Supramolecular assembly of organic dye compounds with J-aggregation leads to a red-shifted absorption spectrum that greatly facilitates the construction of near-infrared (NIR) materials. A considerable improvement of the material functions requires that the absorption red-shift be larger than 100 nm, but such a super-large red-shift is challenging, and the rules leading to the super-large red-shifted absorption is still not explicit. In this review, we focused on those J-aggregated organic dye materials with super-large red-shifted absorption. The nature of the super-large red-shift is originated from the intermolecular charge transfer between neighboring chromophores. The super-large red-shift can be obtained by tuning either the molecular structure or kinetic assembly process in a delicate manner. Materials with super-large red-shifted absorption have been successfully applied to biological imaging, phototherapy, electronic devices, and solar cells, and show great potential in many other fields. The elaboration of assembly induced super-large red-shifted absorption is promising for design of supramolecular NIR materials with tuned structures, enhanced functionalities, and a wide array of applications.
A new black hole X-ray binary (BHXRB) MAXI J1535-571 was discovered by MAXI during its outburst in 2017. Using observations taken by the first Chinese X-ray satellite, the Hard X-ray Modulation Telescope (dubbed as Insight -HXMT), we perform a joint spectral analysis (2-150 keV) in both energy and time domains. The energy spectra provide the essential input for probing the intrinsic Quasi-Periodic Oscillation (QPO) fractional rms spectra (FRS). Our results show that during the intermediate state, the energy spectra are in general consistent with those reported by Swift/XRT and NuSTAR. However, the QPO FRS become harder and the FRS residuals may suggest the presence of either an additional power-law component in the energy spectrum or a turn-over in the intrinsic QPO FRS at high energies.
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