pH-Responsive Near-Infrared Emitting Gold Nanoclusters.

Near-infrared (NIR) fluorophores with pH-responsive properties suggest merits in biological analyses. This work establishes a general and effective method to obtain pH-responsive NIR emissive gold nanoclusters by introducing aliphatic tertiary amine (TA) groups into the ligands. Computational study suggests that the pH-responsive NIR emission is associated with electronic structure change upon protonation and deprotonation of TA groups. Photo-induced electron transfer between deprotonated TA groups and the surface Au-S motifs of gold nanoclusters can disrupt the radiative transitions and thereby decrease the photoluminescence intensity in basic environments (pH=7-11). By contrast, protonated TA groups curb the electron transfer and restore the photoluminescence intensity in acidic environments (pH=4-7). The pH-responsive NIR-emitting gold nanoclusters serve as a specific and sensitive probe for the lysosomes in the cells, offering non-invasive emissions without interferences from intracellular autofluorescence.

Analysis of Silicon Quantum Dots and Serum Proteins Interactions Using Asymmetrical Flow Field-Flow Fractionation.

Semiconductor nanocrystals or quantum dots (QDs) have gained significant attention in biomedical research as versatile probes for imaging, sensing, and therapies. However, the interactions between proteins and QDs, which are crucial for their use in biological applications, are not yet fully understood. Asymmetric flow field-flow fractionation (AF4) is a promising method for analyzing the interactions of proteins with QDs. This technique uses a combination of hydrodynamic and centrifugal forces to separate and fractionate particles based on their size and shape. By coupling AF4 with other techniques, such as fluorescence spectroscopy and multi-angle light scattering, it is possible to determine the binding affinity and stoichiometry of protein-QD interactions. Herein, this approach has been utilized to determine the interaction between fetal bovine serum (FBS) and silicon quantum dots (SiQDs). Unlike metal-containing conventional QDs, SiQDs are highly biocompatible and photostable in nature, making them attractive for a wide range of biomedical applications. In this study, AF4 has provided crucial information on the size and shape of the FBS/SiQD complexes, their elution profile, and their interaction with serum components in real time. The differential scanning microcalorimetric technique has also been employed to monitor the thermodynamic behavior of proteins in the presence of SiQDs. We have investigated their binding mechanisms by incubating them at temperatures below and above the protein denaturation. This study yields various significant characteristics such as their hydrodynamic radius, size distribution, and conformational behavior. The compositions of SiQD and FBS influence the size distribution of their bioconjugates; the size increases by intensifying the concentration of FBS, with their hydrodynamic radii ranging between 150 and 300 nm. The results signify that in the alliance of SiQDs to the system, there is an augmentation of the denaturation point of the proteins and hence their thermal stability, providing a more comprehensive understanding of the interactions between FBS and QDs.

Luminescent Gold Nanocluster-Methylcellulose Composite Optical Fibers with Low Attenuation Coefficient and High Photostability.

Because of their lightweight structure, flexibility, and immunity to electromagnetic interference, polymer optical fibers (POFs) are used in numerous short-distance applications. Notably, the incorporation of luminescent nanomaterials in POFs offers optical amplification and sensing for advanced nanophotonics. However, conventional POFs suffer from nonsustainable components and processes. Furthermore, the traditionally used luminescent nanomaterials undergo photobleaching, oxidation, and they can be cytotoxic. Therefore, biopolymer-based optical fibers containing nontoxic luminescent nanomaterials are needed, with efficient and environmentally acceptable extrusion methods. Here, such an approach for fibers wet-spun from aqueous methylcellulose (MC) dispersions under ambient conditions is demonstrated. Further, the addition of either luminescent gold nanoclusters, rod-like cellulose nanocrystals or gold nanocluster-cellulose nanocrystal hybrids into the MC matrix furnishes strong and ductile composite fibers. Using cutback attenuation measurement, it is shown that the resulting fibers can act as short-distance optical fibers with a propagation loss as low as 1.47 dB cm-1 . The optical performance is on par with or even better than some of the previously reported biopolymeric optical fibers. The combination of excellent mechanical properties (Young's modulus and maximum strain values up to 8.4 GPa and 52%, respectively), low attenuation coefficient, and high photostability makes the MC-based composite fibers excellent candidates for multifunctional optical fibers and sensors.

Dual emitting Ag35 nanocluster protected by 2-pyrene imine thiol.

In this communication, we present the synthesis of 2-pyrene imine thiol (2-PIT)-protected Ag35 nanoclusters using a ligand exchange-induced structural transformation reaction. The formation of the nanocluster and its composition were confirmed through several spectroscopic and electron microscopic studies. The UV-vis absorption spectrum showed a set of characteristic features of the nanocluster. This nanocluster showed blue emission under UV light due to pyrene to metal core charge-transfer, and NIR emission due to charge-transfer within the metal core. This is the first report on dual emitting pyrene protected atomically precise silver nanoclusters.

Transition-Metal-Doped NIR-Emitting Silicon Nanocrystals.

Impurity-doping in nanocrystals significantly affects their electronic properties and diversifies their applications. Herein, we report the synthesis of transition metal (Mn, Ni, Co, Cu)-doped oleophilic silicon nanocrystals (SiNCs) through hydrolysis/polymerization of triethoxysilane with acidic aqueous metal salt solutions, followed by thermal disproportionation of the resulting gel into a doped-Si/SiO2 composite that, upon HF etching and hydrosilylation with 1-n-octadecene, produces free-standing octadecyl-capped doped SiNCs (diameter≈3 to 8 nm; dopant <0.2 atom %). Metal-doping triggers a red-shift of the SiNC photoluminescence (PL) of up to 270 nm, while maintaining high PL quantum yield (26 % for Co doping).

A one-pot synthesis of water soluble highly fluorescent silica nanoparticles.

We report a one-pot synthesis of water dispersible fluorescent silica nanoparticles (NPs) functionalized with terminal amine groups, starting from silicon tetrabromide (SiBr4) and aminopropyltriethoxy silane (APTES). The NPs range from 1 to 2 nm in diameter, and exhibit an intense blue emission with a quantum yield (QY) of around 34% in water. They were characterized using XRD, XPS, TEM and FTIR spectroscopy for structural analysis. A tentative mechanism explaining the origin of the NPs emission in the blue region is presented based on the distinctive features of their low temperature photoluminescence (PL), photoluminescence excitation (PLE) spectrum and time correlated single photon counting lifetime decay profiles. The outstanding PL QY and photostability of the NPs, together with their water dispersibility and biocompatibility, constitute a unique set of properties among existing silica NPs and enable the application of the NPs in various fields.

Origin of the Photoluminescence Quantum Yields Enhanced by Alkane-Termination of Freestanding Silicon Nanocrystals: Temperature-Dependence of Optical Properties.

On the basis of the systematic study on temperature dependence of photoluminescence (PL) properties along with relaxation dynamics we revise a long-accepted mechanism for enhancing absolute PL quantum yields (QYs) of freestanding silicon nanocrystals (ncSi). A hydrogen-terminated ncSi (ncSi:H) of 2.1 nm was prepared by thermal disproportination of (HSiO1.5)n, followed by hydrofluoric etching. Room-temperature PL QY of the ncSi:H increased twentyfold only by hydrosilylation of 1-octadecene (ncSi-OD). A combination of PL spectroscopic measurement from cryogenic to room temperature with structural characterization allows us to link the enhanced PL QYs with the notable difference in surface structure between the ncSi:H and the ncSi-OD. The hydride-terminated surface suffers from the presence of a large amount of nonradiative relaxation channels whereas the passivation with alkyl monolayers suppresses the creation of the nonradiative relaxation channels to yield the high PL QY.

Functional double-shelled silicon nanocrystals for two-photon fluorescence cell imaging: spectral evolution and tuning.

Functional near-IR (NIR) emitting nanoparticles (NPs) adapted for two-photon excitation fluorescence cell imaging were obtained starting from octadecyl-terminated silicon nanocrystals (ncSi-OD) of narrow photoluminescence (PL) spectra having no long emission tails, continuously tunable over the 700-1000 nm window, PL quantum yields exceeding 30%, and PL lifetimes of 300 µs or longer. These NPs, consisting of a Pluronic F127 shell and a core made up of assembled ncSi-OD kept apart by an octadecyl (OD) layer, were readily internalized into the cytosol, but not the nucleus, of NIH3T3 cells and were non-toxic. Asymmetrical field-flow fractionation (AF4) analysis was carried out to determine the size of the NPs in water. HiLyte Fluor 750 amine was linked via an amide link to NPs prepared with Pluronic-F127-COOH, as a first demonstration of functional NIR-emitting water dispersible ncSi-based nanoparticles.

Copper nanoparticle (CuNP) nanochain arrays with a reduced toxicity response: a biophysical and biochemical outlook on Vigna radiata.

Copper deficiency or toxicity in agricultural soil circumscribes a plant's growth and physiology, hampering photochemical and biochemical networks within the system. So far, copper sulfate (CS) has been used widely despite its toxic effect. To get around this long-standing problem, copper nanoparticles (CuNPs) have been synthesized, characterized, and tested on mung bean plants along with commercially available salt CS, to observe morphological abnormalities enforced if any. CuNPs enhanced photosynthetic activity by modulating fluorescence emission, photophosphorylation, electron transport chain (ETC), and carbon assimilatory pathway under controlled laboratory conditions, as revealed from biochemical and biophysical studies on treated isolated mung bean chloroplast. CuNPs at the recommended dose worked better than CS in plants in terms of basic morphology, pigment contents, and antioxidative activities. CuNPs showed elevated nitrogen assimilation compared to CS. At higher doses CS was found to be toxic to the plant system, whereas CuNP did not impart any toxicity to the system including morphological and/or physiological alterations. This newly synthesized polymer-encapsulated CuNPs can be utilized as nutritional amendment to balance the nutritional disparity enforced by copper imbalance.

High throughput electron transfer from carbon dots to chloroplast: a rationale of enhanced photosynthesis.

A biocompatible amine functionalized fluorescent carbon dots were developed and isolated for gram scale applications. Such carbogenic quantum dots can strongly conjugate over the surface of the chloroplast and due to that strong interaction the former can easily transfer electrons towards the latter by assistance of absorbed light or photons. An exceptionally high electron transfer from carbon dots to the chloroplast can directly effect the whole chain electron transfer pathway in a light reaction of photosynthesis, where electron carriers play an important role in modulating the system. As a result, carbon dots can promote photosynthesis by modulating the electron transfer process as they are capable of fastening the conversion of light energy to the electrical energy and finally to the chemical energy as assimilatory power (ATP and NADPH).

Folate conjugated silk fibroin nanocarriers for targeted drug delivery.

Disease treatment processes mainly focus on the development of nontoxic, biodegradable, non-immunogenic, biocompatible materials capable of controlled and long-term release of biomolecules. In this work silk protein fibroin from non-mulberry tropical tasar silkworm, Antheraea mylitta, is used to prepare nanoparticles as a drug delivery system. Folate is a vitamin, which is brought into healthy and cancerous cells by folate receptors. The efficiency of silk fibroin-folate nanoparticles loaded with anticancer drug doxorubicin was evaluated by analysing the cell viability, proliferation and endocytosis. Consequently the effects of pro-inflammatory responses by cytokines such as TNF-α, IL-1ß and nitric oxide were checked by stimulating the macrophages with folate conjugated silk fibroin nanoparticles. The fibroin-folate nanocarriers are nontoxic, easily taken up by cells and capable of sustained drug release. Nanoparticles loaded with anticancer drug doxorubicin target cancer cells. The results show that silk fibroin-folate nanoparticles may serve as promising nanocarriers for different biomedical and nanotechnology applications in cancer research.

Photochemical modulation of biosafe manganese nanoparticles on Vigna radiata: a detailed molecular, biochemical, and biophysical study.

Manganese (Mn) is an essential element for plants which intervenes mainly in photosynthesis. In this study we establish that manganese nanoparticles (MnNP) work as a better micronutrient than commercially available manganese salt, MnSO4 (MS) at recommended doses on leguminous plant mung bean (Vigna radiata) under laboratory condition. At higher doses it does not impart toxicity to the plant unlike MS. MnNP-treated chloroplasts show greater photophosphorylation, oxygen evolution with respect to control and MS-treated chloroplasts as determined by biophysical and biochemical techniques. Water splitting by an oxygen evolving complex is enhanced by MnNP in isolated chloroplast as confirmed by polarographic and spectroscopic techniques. Enhanced activity of the CP43 protein of a photosystem II (PS II) Mn4Ca complex influenced better phosphorylation in the electron transport chain in the case of MnNP-treated chloroplast, which is evaluated by sodium dodecyl sulfate polyacrylamide gel electrophoresis and corresponding Western blot analysis. To the best of our knowledge this is the first report to augment photosynthesis using MnNP and its detailed correlation with different molecular, biochemical and biophysical parameters of photosynthetic pathways. At effective dosage, MnNP is found to be biosafe both in plant and animal model systems. Therefore MnNP would be a novel potential nanomodulator of photochemistry in the agricultural sector.

Luminescent S-doped carbon dots: an emergent architecture for multimodal applications.

A facile route has been developed to synthesise and isolate sulphur doped fluorescent carbon dots for the first time. Such carbogenic quantum dots exhibit a wide band gap of 4.43 eV with a high open circuit voltage (VOC) of 617 mV along with a fill factor (FF) as high as 37%, using phenyl-C60-butyric acid methyl ester (PCBM) as the electron transporting layer. Besides the wide band gap, which is useful in the fabrication of solar cells, sulphur modified carbon dots also exhibit a high fluorescence quantum yield of 11.8% without any additional surface passivation, producing a unique fluorescent probe for further applications. In addition, the particles have a strong tendency to interact with the surface of gold nanoparticles and produce a thin fluorescent layer over their surfaces. Moreover, as they are completely biocompatible in nature, the highly fluorescent S-doped carbon dots have a strong potential for use in bioimaging applications. Interestingly, owing to the presence of oxygen and sulphur functionality, the highly negatively charged particles can easily bind with positively charged DNA-PEI complexes, simply by mixing them, and after interaction with DNA, bright blue fluorescence has been observed under an excitation wavelength of 405 nm .

Fabrication of multi-structure nanocarbons from carbon xerogel: a unique scaffold towards bio-imaging.

A novel route has been developed to fabricate different carbon nanostructures having individual morphology of carbon nanoparticles: nanofullerene, nanocube, nanoleaf and porous nanorods, through the combustion of carbon xerogel with nitric acid. These fabricated nanostructures exhibited bright green fluorescence under the exposure of UV light.

Synthesis, functionalization and bioimaging applications of highly fluorescent carbon nanoparticles.

Highly fluorescent crystalline carbon nanoparticles (CNPs) have been synthesized by one step microwave irradiation of sucrose with phosphoric acid at 100 W for 3 min 40 s. This method is very simple, rapid and economical and hence can be used for large scale applications. The average particle sizes are 3 to 10 nm and they emit bright green fluorescence under the irradiation of UV-light. Therefore, the particles can be used as a unique material for bioimaging as well as drug delivery. To further increase the fluorescence property of the synthetic carbon nanoparticles we simply functionalized them by using different organic dyes, such as fluorescein, rhodamine B and α-naphthylamine; the maximum fluorescence intensity was observed for the particles functionalized with fluorescein. It is very interesting to note that all of those compounds show maximum fluorescence intensity at 225 nm excitation wavelength and for any excitation wavelength the peak positions are exactly same the position as that of CNPs itself, which is completely different from the individual precursors (dyes). All of the above compounds, including CNPs, have also been successfully introduced into the erythrocyte enriched fraction of healthy human blood cells with minimum cytotoxicity.