Nitrogen-functionalized graphene quantum dot incorporated GelMA microgels as fluorescent 3D-tissue Constructs.

Biopolymer microgels present many opportunities in biomedicine and tissue engineering. To understand their in vivo behavior in therapeutic interventions, long-term monitoring is critical, which is usually achieved by incorporating fluorescent materials within the hydrogel matrix. Current research is limited due to issues concerning the biocompatibility and instability of the conventional fluorescent species, which also tend to adversely affect the bio-functionality of the hydrogels. Here, we introduce a microfluidic-based approach to generate nitrogen-functionalized graphene quantum dot (NGQD) incorporated gelatin methacryloyl (GelMA) hydrogel microspheres, capable of long-term monitoring while preserving or enhancing the other favorable features of 3D cell encapsulation. A multilayer droplet-based microfluidic device was designed and fabricated to make monodisperse NGQD-loaded GelMA hydrogel microspheres encapsulating skeletal muscle cells (C2C12). Control over the sizes of microspheres could be achieved by tuning the flow rates in the microfluidic device. Skeletal muscle cells encapsulated in these microgels exhibited high cell viability from day 1 (82.9 ± 6.50%) to day 10 (92.1 ± 3.90%). The NGQD-loaded GelMA microgels encapsulating the cells demonstrated higher metabolic activity compared to the GelMA microgels. Presence of sarcomeric α-actin was verified by immunofluorescence staining on day 10. A fluorescence signal was observed from the NGQD-loaded microgels during the entire period of the study. The investigation reveals the advantages of integrating NGQDs in microgels for non-invasive imaging and monitoring of cell-laden microspheres and presents new opportunities for future therapeutic applications.

Excitation dependence and independence of photoluminescence in carbon dots and graphene quantum dots: insights into the mechanism of emission.

Excitation-dependent, multicolor emission from different varieties of 0D carbon systems has attracted immense research attention. It is generally accepted that some variants of 0D carbon exhibit excitation dependent emission, while other variants do not. A third variant exhibits both excitation dependent as well as excitation independent emission. In this work we investigate the structure, composition, steady-state emission-excitation and photoluminescence decay dynamics of three distinctly different variants of 0D carbon - amorphous carbon dots (aCDs), graphene quantum dots (GQDs) and nitrogen-doped GQDs (NGQDs). We find that despite significant differences in the structure and composition there is a striking similarity in the excitation energy dependence of the emission characteristics of these three different dots. All of them exhibit excitation energy independent emission below some threshold wavelength (λth), and above this threshold the emission becomes excitation dependent. We also demonstrate that a similar trend is apparent for nearly all variants of 0D carbon reported in the literature. The threshold wavelength correlates well with the excitation wavelength for the most intense emission and the photoluminescence excitation peaks, suggesting a common origin of light emission in these carbon dots. The findings provide important clues for developing a unified general picture for understanding the light emission mechanism in 0D carbon nanostructures.

One-Pot Synthesis of Gel Glass Embedded with Luminescent Silicon Nanoparticles.

Preparation of highly luminescent glasses involves expensive and complicated processes and usually requires high temperature. In this work, we show that luminescent silicon (Si) nanoparticle (NP)- embedded silicate gel glasses can be developed under near-ambient conditions by a remarkably simple, one-pot strategy, without using any sophisticated instrumentation or technique. Simultaneous hydrolysis and reduction of (3-aminopropyl)triethoxysilane leads to the formation of colloidal Si nanocrystals that can be transformed to a glassy phase upon slow evaporation followed by freezing. Structural investigations reveal the formation of a sodium silicate gel glass framework having discernible shear bands, along with embedded Si NPs. High photoluminescence quantum yield (ca. 35-40%), low glass-transition temperature ( Tg ≈ 66-73 °C), strain-tolerant mechanical stability, and inexpensive preparation make the glass attractive for applications as display materials and photonic converters.

Amorphous Carbon Dots and their Remarkable Ability to Detect 2,4,6-Trinitrophenol.

Apparently mundane, amorphous nanostructures of carbon have optical properties which are as exotic as their crystalline counterparts. In this work we demonstrate a simple and inexpensive mechano-chemical method to prepare bulk quantities of self-passivated, amorphous carbon dots. Like the graphene quantum dots, the water soluble, amorphous carbon dots too, exhibit excitation-dependent photoluminescence with very high quantum yield (~40%). The origin and nature of luminescence in these high entropy nanostructures are well understood in terms of the abundant surface traps. The photoluminescence property of these carbon dots is exploited to detect trace amounts of the nitro-aromatic explosive - 2,4,6-trinitrophenol (TNP). The benign nanostructures can selectively detect TNP over a wide range of concentrations (0.5 to 200 µM) simply by visual inspection, with a detection limit of 0.2 µM, and consequently outperform nearly all reported TNP sensor materials.

Unipolar resistive switching and tunneling oscillations in isolated Si-SiO x core-shell nanostructure.

Unipolar resistive switching (URS) is observed in isolated Si-SiO x core-shell nanostructures. I-V characteristics recorded by a conductive atomic force microscope tip show SET and RESET processes with self compliance behavior. Hopping of carriers through defect states in the high resistance state (HRS) and space charge limited conduction in the low resistance state (LRS) are found to be the dominant carrier transport mechanisms in Si-SiO x core-shell nanostructures. URS between LRS and HRS may be attributed to the transition between hydrogen bridge (Si-H-Si) and hydrogen doublet (Si-HH-Si) defects. During RESET process, charge carriers tunnel through the nanostructure giving rise to oscillatory conduction.

Highly lattice-mismatched semiconductor-metal hybrid nanostructures: gold nanoparticle encapsulated luminescent silicon quantum dots.

Synthesis of hybrid core-shell nanostructures requires moderate lattice mismatch (<5%) between the materials of the core and the shell and usually results in the formation of structures with an atomically larger entity comprising the core. A reverse situation, where an atomically larger entity encapsulates a smaller atomic radius component having substantial lattice mismatch is unachievable by conventional growth techniques. Here, we report successful synthesis of ultra-small, light-emitting Si quantum dots (QDs) encapsulated by Au nanoparticles (NPs) forming a hybrid nanocomposite that exhibits intense room temperature photoluminescence (PL) and intriguing plasmon-exciton coupling. A facile strategy was adopted to utilize the active surface of oxide etched Si QDs as preferential sites for Au NP nucleation and growth which resulted in the formation of core-shell nanostructures consisting of an atomically smaller Si QD core surrounded by a substantially lattice-mismatched Au NP shell. The PL characteristics of the luminescent Si QDs (quantum yield ∼28%) are dramatically altered following Au NP encapsulation. Au coverage of the bare Si QDs effectively stabilizes the emission spectrum and leads to a red-shift of the PL maxima by ∼37 nm. The oxide related PL peaks observed in Si QDs are absent in the Au treated sample suggesting the disappearance of oxide states and the appearance of Au NP associated Stark shifted interface states within the widened band-gap of the Si QDs. Emission kinetics of the hybrid system show accelerated decay due to non-radiative energy transfer between the Si QDs and the Au NPs and associated quenching in PL efficiency. Nevertheless, the quantum yield of the hybrid remains high (∼20%) which renders these hetero-nanostructures exciting candidates for multifarious applications.

Superparamagnetic iron oxide nanoparticle attachment on array of micro test tubes and microbeakers formed on p-type silicon substrate for biosensor applications.

A uniformly distributed array of micro test tubes and microbeakers is formed on a p-type silicon substrate with tunable cross-section and distance of separation by anodic etching of the silicon wafer in N, N-dimethylformamide and hydrofluoric acid, which essentially leads to the formation of macroporous silicon templates. A reasonable control over the dimensions of the structures could be achieved by tailoring the formation parameters, primarily the wafer resistivity. For a micro test tube, the cross-section (i.e., the pore size) as well as the distance of separation between two adjacent test tubes (i.e., inter-pore distance) is typically approximately 1 µm, whereas, for a microbeaker the pore size exceeds 1.5 µm and the inter-pore distance could be less than 100 nm. We successfully synthesized superparamagnetic iron oxide nanoparticles (SPIONs), with average particle size approximately 20 nm and attached them on the porous silicon chip surface as well as on the pore walls. Such SPION-coated arrays of micro test tubes and microbeakers are potential candidates for biosensors because of the biocompatibility of both silicon and SPIONs. As acquisition of data via microarray is an essential attribute of high throughput bio-sensing, the proposed nanostructured array may be a promising step in this direction.

Free standing luminescent silicon quantum dots: evidence of quantum confinement and defect related transitions.

We report the synthesis of luminescent, free standing silicon quantum dots by dry and wet etching of silicon and silicon oxide core/shell nanostructures, which are synthesized by controlled oxidation of mechanically milled silicon. Dry and wet etching performed with CF(4) plasma and aqueous HF, respectively, result in the removal of the thick oxide shell of the core/shell nanostructures and affect an additional step of size reduction. HF etch is capable of producing isolated, spherical quantum dots of silicon with dimensions ∼ 2 nm. However, the etching processes introduce unsaturated bonds at the surface of the nanocrystals which are subsequently passivated by oxygen on exposure to ambient atmosphere. The photoluminescence spectra of the colloidal suspensions of these nanocrystals are characterized by double peaks and excitation dependent shift of emission energy. Comparison of the structural, absorption and luminescence characteristics of the samples provides evidence for two competing transition processes--quantum confinement induced widened band gap related transitions and oxide associated interface state mediated transitions. The results enable us to experimentally distinguish between the contributions of the two different transition mechanisms, which has hitherto been a challenging problem.