Project description:Unmodified single-stranded DNA has recently gained popularity for the templated synthesis of fluorescent noble metal nanoclusters (NCs). Bright, stable, and biocompatible clusters have been developed primarily through optimization of DNA sequence. However, DNA backbone modifications have not yet been investigated. In this work, phosphorothioate (PS) DNAs are evaluated in the synthesis of Au and Ag nanoclusters, and are employed to successfully template a novel emitter using T15 DNA at neutral pH. Mechanistic studies indicate a distinct UV-dependent formation mechanism that does not occur through the previously reported thymine N3. The positions of PS substitution have been optimized. This is the first reported use of a T15 template at physiological pH for AgNCs.
Project description:A new strategy using silver nanoparticles (Ag NPs) to synthesize thiolated Au NCs is demonstrated. The quasi-spherical Ag NPs serve as a platform, functioning as a reducing agent for Au (III) and attracting capping ligands to the surface of the Ag NPs. Glutathione disulfide (GSSG) and dithiothreitol (DTT) were used as capping ligands to synthesize thiolated Au NCs (glutathione-Au NCs and DTT-Au NCs). The glutathione-Au NCs and DTT-Au NCs showed red color luminance with similar emission wavelengths (630 nm) at an excitation wavelength of 354 nm. The quantum yields of the glutathione-Au NCs and DTT-Au NCs were measured to be 7.3% and 7.0%, respectively. An electrophoretic mobility assay showed that the glutathione-Au NCs moved toward the anode, while the DTT-Au NCs were not mobile under the electric field, suggesting that the total net charge of the thiolated Au NCs is determined by the charges on the capping ligands. The detection of the KSV values, 26 M-1 and 0 M-1, respectively, revealed that glutathione-Au NCs are much more accessible to an aqueous environment than DTT-Au NCs.
Project description:In the present work, we have synthesized water soluble Ag nanoclusters using PMAA as a template with different Ag+: COO-ratios, to optimize it for highest brightness using less UV exposure time. Fluorescence polarization was 0.30 for and was found to vary with excitation and emission wavelength with few hundred picoseconds average fluorescence lifetime. Fluorescence Correlation Spectroscopy data depicts slower diffusion at red excitation compared to blue excitation in confocal volume than conventionally synthesized colloids proving presence of multiple sizes. The optical properties of the particles are dependent upon the excitation wavelength used and the emission wavelength collected.
Project description:Here, we demonstrate through AFM imaging and CD spectroscopy that the binding of silver ions (Ag+) to poly(dGdC), a double-stranded (ds) DNA composed of two identical repeating strands, at a stoichiometry of one Ag+ per GC base pair induces a one-base shift of one strand relative to the other. This results in a ds nucleic acid-Ag+ conjugate consisting of alternating CC and GG base pairs coordinated by silver ions. The proposed organization of the conjugate is supported by the results of our Quantum Mechanical (QM) and Molecular Mechanics (MMs) calculations. The reduction of Ag+ ions followed by the partial oxidation of silver atoms yields a highly fluorescent conjugate emitting at 720 nm. This fluorescent behavior in conjugates of long, repetitive ds DNA (thousands of base pairs) with silver has never been demonstrated before. We propose that the poly(dGdC)-Ag conjugate functions as a dynamic system, comprising various small clusters embedded within the DNA and interacting with one another through energy transfer. This hypothesis is supported by the results of our QM and MMs calculations. Additionally, these DNA-silver conjugates, comprising silver nanoclusters, may possess conductive properties, making them potential candidates for use as nanowires in nanodevices and nanosensors.
Project description:The encapsulation of Cu nanoclusters (Cu NCs) in metal-organic frameworks (MOFs) would improve the properties of Cu NCs. So far, these composites were reported by a two-step synthesis process. In this work, a facile one-pot synthesis of hybridization of glutathione (GSH) protected Cu NCs (Cu NCs@GSH) and MOF-5 (Cu NCs@GSH/MOFs) composites was reported for the first time. The results of UV-vis, TEM, XPS and SEM proved Cu NCs@GSH were distributed homogeneously over the entire MOF structure. The fluorescence intensity of Cu NCs encapsulated in MOF-5 was enhanced about 35-fold owing to the confining scaffold of the MOF and the stability was extended from 3 days to 3 months. Cu NCs@GSH/MOFs composites exhibited strong orange fluorescence and the emissions could change between blue, orange and red as they were partially reversible in different pH environments. This one-pot synthetic strategy could be extended for the encapsulation of fluorescent Ag NCs in MOFs as well. As-prepared Cu NCs@GSH/MOF-5 composites had high stability, and were easily recycled by centrifugation in aqueous solution, therefore, it would be utilized to develop a reusable sensor for detection of metal ions in the future.
Project description:Fluorescent silver nanoclusters (Ag NCs) that are capable of emitting green light have been synthesized using a peptide derived from the C terminal of silk fibroin heavy chain (CSH) via a one-pot, green, and facile synthesis method. The emission was also found to be stable at the excitation wavelength and the fluorescence quantum yield of Ag NCs was measured to be 1.1%. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF MS) indicated the presence of a range of Ag species that correspond to Ag1, Ag2, Ag3 and Ag4. Transmission electron microscopic analyses suggested that the formed particles are uniform and well dispersive with an average diameter of 2.5 nm. The Ag NCs were successfully applied to cell imaging in murine preosteoblast MC3T3-E1 cells. Finally, Ag NCs observed by MTT exhibited distinct cytotoxicity at CSH-Ag NCs concentrations of 600 μM. Based on the concept of utilizing a functional peptide from nature, this study demonstrates a novel approach to fabricate aqueous metal nanoclusters for tracking applications in bioimaging.
Project description:Noble metal nanoclusters are ultrasmall nanomaterials with tunable properties and huge application potential; however, retaining their enhanced functionality is difficult as they readily lose their properties without stabilization. Here, we demonstrate a facile synthesis of highly photostable silver nanoclusters in a polymer thin film using visible light photoreduction. Furthermore, the different stages of the nanocluster formation are investigated in detail using absorption and fluorescence spectroscopy, fluorescence microscopy, and atomic force microscopy. A cost-effective fabrication of photostable micron-sized fluorescent silver nanocluster barcode is demonstrated in silver-impregnated polymer films using a low-power continuous-wave laser diode. It is shown that a laser power of as low as 0.75 mW is enough to write fluorescent structures, corresponding to the specifications of a commercially available laser pointer. The as-formed nanocluster-containing microstructures can be useful in direct labeling applications such as authenticity marking and fluorescent labeling.
Project description:Metal nanomaterials have been reported as effective absorbents for the removal of pollutants in the water system, but the release of ions from these nanomaterials brings another concern. Herein, silver nanoclusters (AgNCs) were encapsulated in porous metal-organic frameworks of ZIF-8 (MOF-AgNCs). Compared to AgNCs, the release of Ag+ significantly decreases from MOF-AgNCs, indicating that the product presents a lower threat to the environment. The MOF-AgNCs were employed for the rapid removal of heavy metals, such as Pb2+ and Mn2+, from water. The mechanism and removal efficiencies were investigated.
Project description:Metal nanoclusters (NCs) have emerged as a promising class of fluorescent probes for cellular imaging due to their high resistance to photobleaching and low toxicity. Nevertheless, their widespread use in clinical diagnosis is limited by their unstable intracellular fluorescence. In this study, we develop an intracellularly biosynthesized fluorescent probe, DNA nanoribbon-gold NCs (DNR/AuNCs), for long-term cellular tracking. Our results show that DNR/AuNCs exhibit a 4-fold enhancement of intracellular fluorescence intensity compared to free AuNCs. We also investigated the mechanism underlying the fluorescence enhancement of AuNCs by DNRs. Our findings suggest that the higher synthesis efficiency and stability of AuNCs in the lysosome may contribute to their fluorescence enhancement, which enables long-term (up to 15 days) fluorescence imaging of cancer cells (enhancement of ∼60 times compared to free AuNCs). Furthermore, we observe similar results with other metal NCs, confirming the generality of the DNR-assisted biosynthesis approach for preparing highly bright and stable fluorescent metal NCs for cancer cell imaging.
Project description:Excessive administration of penicillin G and improper disposal of its residues pose a serious risk to human health; therefore, the development of convenient methods for monitoring penicillin G levels in products is essential. Herein, novel gold-silver nanoclusters (AuAgNCs) were synthesized using chicken egg white and 6-aza-2-thiothymine as dual ligands with strong yellow fluorescence at 509 and 689 nm for the highly selective detection of penicillin G. The AuAgNCs were characterized using transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet-visible absorption spectrophotometry, and fluorescence spectrophotometry. Under optimum conditions, the fluorescence intensity decreased linearly with the concentration of penicillin G from 0.2 to 6 μM, with a low detection limit of 18 nM. Real sample analyses indicated that a sensor developed using the AuAgNCs could detect penicillin G in urine and water samples within 10 min, with the recoveries ranging from 99.7 to 104.0%. The particle size of the AuAgNCs increased from 1.80 to 9.06 nm in the presence of penicillin G. We believe the aggregation-induced quenching of the fluorescence of the AuAgNCs was the main mechanism for the detection of penicillin G. These results demonstrate the ability of our sensor for monitoring penicillin G levels in environmental and clinic samples.