There are only a few systematic rules about how to selectively control the formation of DNA-templated metal nanoparticles (NPs) by varying sequence combinations of double-stranded DNA (dsDNA), although many attempts have been made. Herein, we develop a facile method for sequence-dependent formation of fluorescent CuNPs by using dsDNA as templates. Compared with random sequences, AT sequences are better templates for highly fluorescent CuNPs. Other specific sequences, for example, GC sequences, do not induce the formation of CuNPs. These results shed light on directed DNA metallization in a sequence-specific manner. Significantly, both the fluorescence intensity and the fluorescence lifetime of CuNPs can be tuned by the length or the sequence of dsDNA. In order to demonstrate the promising practicality of our findings, a sensitive and label-free fluorescence nuclease assay is proposed.

Developing plasmon‐enhanced fluorescence (PEF) technology for identifying important biological molecules has a profound impact on biosensing and bioimaging. However, exploration of PEF for biological application is still at a very early stage. Herein, novel PEF‐based core–shell nanostructures as a near‐infrared fluorescent turn‐on sensor for highly sensitive and selective detection of pyrophosphate (PPi) in aqueous solution are proposed. This nanostructure gold nanorod (AuNR)@SiO2@meso‐tetra(4‐carboxyphenyl) porphyrin (TCPP) contains a gold nanorod core with an aspect ratio of 2.3, a silica shell, and TCPP molecules covalently immobilized onto the shell surface. The silica shell is employed a rigid spacer for precisely tuning the distance between AuNR and TCPP and an optimum fluorescence enhancement is obtained. Due to the quenching effect of Cu2+, the copper porphyrin (TCPP‐Cu2+) results in a weak fluorescence. In the presence of PPi, the strong affinity between Cu2+ and PPi can promote the disassembly of the turn‐off state of TCPP‐Cu2+ complexes, and therefore the fluorescence can be readily restored. By virtue of the amplified fluorescence signal imparted by PEF, this nanosensor obtains a detection limit of 820 × 10−9m of PPi with a good selectivity over several anions, including phosphate. Additionally, the potential applicability of this sensor in cell imaging is successfully demonstrated.

Optical antennas with anisotropic metal nanostructures are widely used in the field of fluorescence enhancement based on localized surface plasmons (LSPs). They overcome the intrinsic defects of low brightness of near-infrared (NIR) dyes and can be used to develop sensitive NIR sensors for bioapplications. Here, we demonstrate a novel NIR plasmon-enhanced fluorescence (PEF) system consisting of elongated gold nanobipyramids (Au NBPs) antennas, silica, and NIR dyes. Silica was chosen as the rigid spacer to regulate the distance between the metal nanostructures and dyes. Maximum enhancement was observed at a distance of approximately 17 nm. The enhanced fluorescence could be quenched by Cu and recovered by pyrophosphate (PPi) owing to the strong affinity between PPi and Cu. Thus, the Au NBP@SiO@Cy7 nanoparticles (NPs) detect PPi via "switch-on" fluorescence signals, with a detection limit of 80 nM in the aqueous phase. The probe not only detects PPi in living cells but also can be used for a microRNA assay with a detection limit of 8.4 pM by detecting PPi in rolling circle amplification (RCA). Additionally, gold nanorods (Au NRs) with the same longitudinal plasmon resonance wavelength (LPRW) as the Au NBPs were prepared to synthesize Au NR@SiO@Cy7 NPs for comparison. The experimental and finite-different time-domain (FDTD) simulation results indicate that the stronger electric fields of Au NBPs contribute to a fluorescence enhancement that is several times higher than that of Au NRs, confirming the superior properties of Au NBPs as novel ideal substrates to develop PEF biosensors.

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Monodisperse and water-soluble Cys-Au dots with near-infrared emission successfully prepared by a one-pot synthesis approach, and the as-prepared Au dots could be used for long-term tumor cell imaging and highly selective detecting Pb2+.

Plasmon-enhanced fluorescence (PEF)-based anisotropic nanostructures are considered extremely promising tools for improving the inherent problems of traditional fluorophores and for detecting important biomolecules with high sensitivity. Herein, a novel triangular gold nanoprism (AuNPR)-based fluorescence probe, AuNPR@SiO@12,17-tetramethyl-3-dihydro-(2s-trans)-thyl-7(Ce6), was developed for PEF by virtue of multiple "hot spots" of AuNPRs. Fluorescence enhancement of fluorophores can be realized owing to the larger and stronger electromagnetic fields located at the sharp tips of AuNPRs than those on spherical particles and nanorods. A silica shell was employed as a rigid spacer to precisely adjust the distance between the AuNPR and Ce6 for optimal PEF. Owing to the improved fluorescence signal, core-shell PEF-based AuNPRs can be applied as a turn-on probe for highly selective and sensitive detection of pyrophosphate (PPi) with a desirable detection limit of 0.2 μM using a displacement approach. Meanwhile, we demonstrated that these nanomaterials have great potential for real-time monitoring of polymerase chain reaction (PCR) products, successfully revealing an approximately 240 times higher detectable fluorescence response than that of traditional gel electrophoresis. Furthermore, cell imaging indicates the potential applications of PEF-based probes in living cells.

Streptonigrin methylesterase A (StnA) is one of the tailoring enzymes that modify the aminoquinone skeleton in the biosynthesis pathway of Streptomyces species. Although StnA has no significant sequence homology with the reported α/β-fold hydrolases, it shows typical hydrolytic activity in vivo and in vitro. In order to reveal its functional characteristics, the crystal structures of the selenomethionine substituted StnA (SeMet-StnA) and the complex (S185A mutant) with its substrate were resolved to the resolution of 2.71 Å and 2.90 Å, respectively. The overall structure of StnA can be described as an α-helix cap domain on top of a common α/β hydrolase domain. The substrate methyl ester of 10′-demethoxystreptonigrin binds in a hydrophobic pocket that mainly consists of cap domain residues and is close to the catalytic triad Ser185-His349-Asp308. The transition state is stabilized by an oxyanion hole formed by the backbone amides of Ala102 and Leu186. The substrate binding appears to be dominated by interactions with several specific hydrophobic contacts and hydrogen bonds in the cap domain. The molecular dynamics simulation and site-directed mutagenesis confirmed the important roles of the key interacting residues in the cap domain. Structural alignment and phylogenetic tree analysis indicate that StnA represents a new subfamily of lipolytic enzymes with the specific binding pocket located at the cap domain instead of the interface between the two domains.