Reversible plasmonic circular dichroism (CD) responses are realized for the first time based on temperature-dependent assembly and disassembly of Au nanorod (Au NR) and DNA hybrids. Compared with the conventional UV-vis absorption spectra, the changes in both intensity and line shape of plasmonic CD signals are much more pronounced, leading to a preliminary detection limit of DNA as low as 75 nM. The mechanism and influence factors of reversible plasmonic CD responses are explored.
The manipulation of the chirality and corresponding optical activity in the visible-near-infrared (NIR) light region is significant to realize applications in the fields of chemical sensing, enantioselective separation, chiral nanocatalysis, and optical devices. We studied the plasmon-induced circular dichroism (CD) response by one-dimensional (1D) assembly of cysteine (CYS) and gold nanorods (GNRs). Typically, GNRs can form end-to-end assembly through the electrostatic attraction of CYS molecules preferentially attached on the ends of different GNRs. CD responses are observed at both the UV and visible-NIR light region in the 1D assembly, which are assigned to the CYS molecules and the GNRs, respectively. In addition, the wavelength of the CD responses can be manipulated from 550 nm to more than 900 nm through altering the aspect ratios of GNRs in 1D assembly. Anisotropic enhancement of optical activity is discovered, suggesting that the enhancement of the longitudinal localized surface plasmon resonance (LSPR) peak of GNRs in the CD response is much more apparent than that of the transverse LSPR. The CD responses of individual CYS-attached GNRs and CYS-assembled gold nanoparticles (GNPs) substantiate that the form of assembly and the shape of building blocks are significant not only for the intensity but for the line shape of the CD signals.
The design and fabrication of chiral nanostructures is a promising approach to realize enantiomeric recognition and separation. In our work, gold nanorod@chiral mesoporous silica core-shell nanoparticles (GNR@CMS NPs) have been successfully synthesized. This novel material exhibits strong and tunable circular dichroism signals in the visible and near-infrared regions due to the optical coupling between the CMS shells and the GNR cores. When chiral cysteine molecules are loaded in the porous shells, the corresponding surface enhanced Raman scattering spectroscopy demonstrates a distinct chiral recognition effect, which can be used to semiquantitatively measure the composition of chiral enantiomers. A detailed sensing mechanism has been disclosed by density functional theory calculations.
Here we report that easily obtained per-ethylated pillar[6]arene (EtP6) is a new adsorbent for iodine capture with high chemical and thermal stability. Nonporous EtP6 solids are shown to capture not only volatile iodine in the air but also iodine dissolved in an organic solvent and aqueous solution. Uptake of iodine leads to a structural transformation of EtP6 in the solid state. In the single crystal structure of iodine-doped EtP6 (I@EtP6), each adsorbed iodine molecule is located between two adjacent EtP6 molecules to form a linear supramolecular polymer. Iodine is released spontaneously from I@EtP6 solids when they are immersed in cyclohexane. These EtP6 solids can be reused many times without losing iodine capture capacity.
Fluorescent supramolecular polymeric materials are rising stars in the field of fluorescent materials not only because of the inherent optoelectronic properties originating from their chromophores, but also due to the fascinating stimuli-responsiveness and reversibility coming from their noncovalent connections. Especially, these noncovalent connections influence the fluorescence properties of the chromophores because their state of aggregation and energy transfer can be regulated by the assembly-disassembly process. Considering these unique properties, fluorescent supramolecular polymeric materials have facilitated the evolution of new materials useful for applications in fluorescent sensors, probes, as imaging agents in biological systems, light-emitting diodes, and organic electronic devices. In this Review, fluorescent supramolecular polymeric materials are classified depending on the types of main driving forces for supramolecular polymerization, including multiple hydrogen bonding, electrostatic interactions, π-π stacking interactions, metal-coordination, van der Waals interactions and host-guest interactions. Through the summary of the studies about fluorescent supramolecular polymeric materials, the status quo of this research field is assessed. Based on existing challenges, directions for the future development of this field are furnished.
Assemblies of chiral cysteine (CYS) and Au nanorods (GNRs) are constructed in two typical patterns, end-to-end and side-by-side. Impressively, side-by-side assembled GNRs with CYS show obviously stronger plasmonic circular dichrosim (CD) response compared with the end-to-end assemblies. The corresponding theoretical calculation elucidates the intrinsic relationship among geometric structure, electromagnetic interaction, and induced plasmonic CD of the assemblies. This work will significantly benefit the design and application of plasmonic nanodevices with controllable chiroptical responses.
A novel strategy of dual steric hindrance, which was obtained by Janus modification of gold nanoparticles (Au NPs) and volume exclusion of DNA, was adopted to prepare mono-DNA-modified Au NPs. The yield of mono-DNA-functionalized Au NPs significantly improved from 44 to 70% in the reaction between Au NPs and thiolated DNA. Furthermore, the specificity of mono-DNA-functionalized Au NPs was enhanced from 57 to 95%. The as-prepared Au NPs without postsynthetic treatment showed good controllability in self-assembly fabrication of complex nanostructures.
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