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Currently, the chiral ligand-directed growth strategy has been predominantly employed for preparing chiral gold nanoparticles (AuNPs). In this work, we report the unexpected discovery of homochiral AuNP formation under cryogenic conditions (0 °C) without chiral ligand induction. Systematic investigations revealed significant temperature-dependent evolution of nanoparticle morphology and chiroptical properties across a broad thermal range (-10 to 75 °C). Notably, AuNPs synthesized at 0 °C exhibited a 4.2-fold enhancement in the extinction dissymmetry factor (-factor) compared to those prepared at 60 °C. We propose a temperature-modulated crystallization mechanism governing chiral symmetry breaking during nanoparticle growth. The 0 °C-synthesized chiral AuNPs demonstrated exceptional enantioselective recognition capabilities, particularly as colorimetric probes for glutamine (Gln) enantiomer discrimination. This work developed a chiral ligand-free synthesis method for chiral AuNPs. Our findings establish temperature engineering as a crucial parameter for controlling nanoscale chirality and open new avenues for designing chiral plasmonic materials.
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http://dx.doi.org/10.1021/acs.inorgchem.5c01147 | DOI Listing |
Dalton Trans
September 2025
Department of Chemistry, IIT Kharagpur, Kharagpur, 721302, India.
The solid-solution alloys of Mn-Zn-Ga and Mn-Zn-Sn have been synthesized by a high-temperature method and structurally characterized by X-ray diffraction studies. The substitutional solid-solution alloys that crystallize in the chiral space group 432 or 432 adopt the A13-type structure (β-Mn). Similar to β-Mn, the 20 atoms in the cubic unit cell are distributed over 8 and 12 Wyckoff positions.
View Article and Find Full Text PDFPhilos Trans A Math Phys Eng Sci
September 2025
Research Institute for Mathematical Sciences, Kyoto University, Kyoto, Japan.
Transport phenomena of microswimmers in fluid flows play a crucial role in various biological processes, including bioconvection and cell sorting. In this article, we investigate the dispersion behaviour of chiral microswimmers in a simple shear flow using the generalized Taylor dispersion theory, inspired by biased locomotion of bacterial rheotaxis swimmers. We thus focused on the influence of shear-induced torque effects due to particle chirality, employing an extended Jeffery equation for individual deterministic dynamics.
View Article and Find Full Text PDFOrg Biomol Chem
September 2025
MOE Key Laboratory of Functional Molecular Solids, Anhui Laboratory of Molecule-Based Materials, Institute of Organic Chemistry, College of Chemistry and Materials Science, Anhui Normal University, 189 South Jiuhua Road, Wuhu, Anhui 241002, China.
The enantioselective kinetic resolution of racemic 2-ethynylaziridines ring opening with amines is realized under the catalysis of a chiral Cu(I)-bisphosphine combination. This protocol provides an expedient way to access synthetically valuable enantioenriched propargylic vicinal diamines (70%-95% yields, 14%-95% ee) and 2-ethynylaziridines (70%-95% recovery rates, 14%-95% ee) within 15-240 h under mild reaction conditions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
College of Chemistry and Materials Science, Northwest University, Xi'an, 710069, P.R. China.
Developing artificial hosts with temperature-driven conformational switching behaviors facilitates our understanding of the temperature-dependent allostery and adaptation mechanisms in natural recognition systems. Herein, we report the design and synthesis of three pairs of water-soluble, enantiomeric binaphthalene-based tetraimidazolium macrocycles (SS/RR-1•4Cl- - SS/RR-3•4Cl-) as artificial hosts for exploring sequence-selective recognition of dinucleotides in aqueous media. Owing to the reversible rotational conformation of axially chiral binaphthyl units, SS-1•4Cl- demonstrates the conformational switching, converting from cis-conformation (SS-1) to trans-conformation (SS-1) by increasing temperature, thereby causing the recognition cavity to transition from a closed to an open state.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2025
Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK.
We present a study of the ability of our recently reported well-defined crown ether-coordinated alkali metal phosphides 1 to catalyze hydrophosphination (HP) of alkynes and alkenes. In a comparative study including reaction monitoring by H NMR spectroscopy, we show that the activity of caesium compound 1 greatly exceeds that of its lighter congeners, enabling us to solve some reported challenges of catalytic hydrophosphination. Through the rarely used application of dialkyl phosphines, we were able to produce trialkyl phosphines from HP of styrene derivatives and activated as well as non-activated alkynes by catalytic HP with BuPH and BuPH.
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