The origin of the near-infrared photoluminescence
(PL) from thiolate-protected
gold nanoclusters (Au NCs, <2 nm) has long been controversial,
and the exact mechanism for the enhancement of quantum yield (QY)
in many works remains elusive. Meanwhile, based upon the sole steady-state
PL analysis, it is still a major challenge for researchers to map
out a definitive relationship between the atomic structure and the
PL property and understand how the Au(0) kernel and Au(I)–S
surface contribute to the PL of Au NCs. Herein, we provide a paradigm
study to address the above critical issues. By using a correlated
series of “mono-cuboctahedral kernel” Au NCs and combined
analyses of steady-state, temperature-dependence, femtosecond transient
absorption, and Stark spectroscopy measurements, we have explicitly
mapped out a kernel-origin mechanism and clearly elucidate the surface–structure
effect, which establishes a definitive atomic-level structure–emission
relationship. A ∼100-fold enhancement of QY is realized via
suppression of two effects: (i) the ultrafast kernel relaxation and
(ii) the surface vibrations. The new insights into the PL origin,
QY enhancement, wavelength tunability, and structure–property
relationship constitute a major step toward the fundamental understanding
and structural-tailoring-based modulation and enhancement of PL from
Au NCs.
Silicon nanoparticles (NPs) have been widely accepted as an alternative material for typical quantum dots and commercial organic dyes in light-emitting and bioimaging applications owing to silicon's intrinsic merits of least toxicity, low cost, and high abundance. However, to date, how to improve Si nanoparticle photoluminescence (PL) performance (such as ultrahigh quantum yield, sharp emission peak, high stability) is still a major issue. Herein, we report surface nitrogen-capped Si NPs with PL quantum yield up to 90% and narrow PL bandwidth (full width at half-maximum (fwhm) ≈ 40 nm), which can compete with commercial dyes and typical quantum dots. Comprehensive studies have been conducted to unveil the influence of particle size, structure, and amount of surface ligand on the PL of Si NPs. Especially, a general ligand-structure-based PL energy law for surface nitrogen-capped Si NPs is identified in both experimental and theoretical analyses, and the underlying PL mechanisms are further discussed.
Silk and silk fibroin, the biomaterial from nature, nowadays are being widely utilized in many cutting-edge micro/nanodevices/systems via advanced micro/nanofabrication techniques. Herein, for the first time to our knowledge, we report aqueous multiphoton lithography of diversiform-regenerated-silk-fibroin-centric inks using noncontact and maskless femtosecond laser direct writing (FsLDW). Initially, silk fibroin was FsLDW-crosslinked into arbitrary two/three-dimensional micro/nanostructures with good elastic properties merely using proper photosensitizers. More interestingly, silk/metal composite micro/nanodevices with multidimension-controllable metal content can be FsLDW-customized through laser-induced simultaneous fibroin oxidation/crosslinking and metal photoreduction using the simplest silk/Ag+ or silk/[AuCl4]− aqueous resists. Noticeably, during FsLDW, fibroin functions as biological reductant and matrix, while metal ions act as the oxidant. A FsLDW-fabricated prototyping silk/Ag microelectrode exhibited 104-Ω−1 m−1-scale adjustable electric conductivity. This work not only provides a powerful development to silk micro/nanoprocessing techniques but also creates a novel way to fabricate multifunctional metal/biomacromolecule complex micro/nanodevices for applications such as micro/nanoscale mechanical and electrical bioengineering and biosystems.
In the field of electrochemical detection, ferrocene has a promising application prospect in view of its impact as a component of molecular receptors and sensing materials. In this review, we aim to describe the principle of ferrocene-based electrochemical detection and further discuss its design and performances. In particular, two forms of detection, molecular recognition and sensing systems, were specified. Ferrocene-based molecular receptors with all kinds of structures covering derivatives, polymers, and supramolecular receptors are presented. Benefits of their structures to the recognition behavior are compared and discussed. In electrochemical sensors, the ferrocenecontaining component is used as a mediator or a label. The architectural design, enhancement effect of additives, and the structures of ferrocene-containing components in the corresponding sensors are discussed in this review. Among sensors with different structures, film-type, sandwich-type, and displacement-type sensors are the main architecturally designed sensors. In addition, auxiliary materials such as conducting carbon materials (carbon nanotubes, graphene, and graphene oxide), nanoparticles (magnetic nanoparticles and gold nanoparticles), and modified saccharides which provide synergy in the conductivity and biocompatibility for ferrocene-containing sensors will be discussed as well.
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