The effect of gold nanoparticles (AuNPs) on the polymerization of tubulin has not been examined till now. We report that interaction of weakly protected AuNPs with microtubules (MTs) could cause inhibition of polymerization and aggregation in the cell free system. We estimate that single citrate capped AuNPs could cause aggregation of ∼10(5) tubulin heterodimers. Investigation of the nature of inhibition of polymerization and aggregation by Raman and Fourier transform-infrared (FTIR) spectroscopies indicated partial conformational changes of tubulin and microtubules, thus revealing that AuNP-induced conformational change is the driving force behind the observed phenomenon. Cell culture experiments were carried out to check whether this can happen inside a cell. Dark field microscopy (DFM) combined with hyperspectral imaging (HSI) along with flow cytometric (FC) and confocal laser scanning microscopic (CLSM) analyses suggested that AuNPs entered the cell, caused aggregation of the MTs of A549 cells, leading to cell cycle arrest at the G0/G1 phase and concomitant apoptosis. Further, Western blot analysis indicated the upregulation of mitochondrial apoptosis proteins such as Bax and p53, down regulation of Bcl-2 and cleavage of poly(ADP-ribose) polymerase (PARP) confirming mitochondrial apoptosis. Western blot run after cold-depolymerization revealed an increase in the aggregated insoluble intracellular tubulin while the control and actin did not aggregate, suggesting microtubule damage induced cell cycle arrest and apoptosis. The observed polymerization inhibition and cytotoxic effects were dependent on the size and concentration of the AuNPs used and also on the incubation time. As microtubules are important cellular structures and target for anti-cancer drugs, this first observation of nanoparticles-induced protein's conformational change-based aggregation of the tubulin-MT system is of high importance, and would be useful in the understanding of cancer therapeutics and safety of nanomaterials.
The development of luminescent mercury sulfide quantum dots (HgS QDs) through the bio-mineralization process has remained unexplored. Herein, a simple, two-step route for the synthesis of HgS quantum dots in bovine serum albumin (BSA) is reported. The QDs are characterized by UV-vis spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, luminescence, Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), circular dichroism (CD), energy dispersive X-ray analysis (EDX), and picosecond-resolved optical spectroscopy. Formation of various sizes of QDs is observed by modifying the conditions suitably. The QDs also show tunable luminescence over the 680-800 nm spectral regions, with a quantum yield of 4-5%. The as-prepared QDs can serve as selective sensor materials for Hg(II) and Cu(II), based on selective luminescence quenching. The quenching mechanism is found to be based on Dexter energy transfer and photoinduced electron transfer for Hg(II) and Cu(II), respectively. The simple synthesis route of protein-capped HgS QDs would provide additional impetus to explore applications for these materials.
Steeping interest on graphene research in basic sciences and applications emphasizes the need for an economical means of synthesizing it. We report a method for the synthesis of graphene on commercially available stainless steel foils using direct thermal chemical vapor deposition. Our method of synthesis and the use of relatively cheap precursors such as ethanol (CH 3 CH 2 OH) as a source of carbon and SS 304 as the substrate, proved to be economically viable. Presence of singleand few-layer graphene was confirmed using confocal Raman microscopy/spectroscopy. X-ray photoelectron spectroscopic measurements were further used to establish the influence of various elemental species present in stainless steel on graphene growth. Role of cooling rate on surface migration of certain chemical species (oxides of Fe, Cr and Mn) that promote or hinder the growth of graphene is probed. Such analysis of the chemical species present on the surface can be promising for graphene based catalytic research.
We report an in situ Raman spectroscopic and microscopic investigation of the electrochemical unzipping of single-walled carbon nanotubes (SWNTs). Observations of the radial breathing modes (RBMs) using Raman spectral mapping reveal that metallic SWNTs are opened up rapidly followed by gradual unzipping of semiconducting SWNTs. Consideration of the resonant Raman scattering theory suggests that two metallic SWNTs with chiralities (10, 4) and (12, 0) get unzipped first at a lower electrode potential (0.36 V) followed by the gradual unzipping of another two metallic tubes, (9, 3) and (10, 1), at a relatively higher potential (1.16 V). The semiconducting SWNTs with chiralities (11, 7) and (12, 5), however, get open up gradually at ±1.66 V. A rapid decrease followed by a subsequent gradual decrease in the metallicity of the SWNT ensemble as revealed from a remarkable variation of the peak width of the G band complies well with the variations of RBM. Cyclic voltammetry also gives direct evidence for unzipping in terms of improved capacitance after oxidation followed by more important removal of oxygen functionalities during the reduction step, as reflected in subtle changes of the morphology confirming the formation of graphene nanoribbons. The density functional-based tight binding calculations show additional dependence of chirality and diameter of nanotubes on the epoxide binding energies, which is in agreement with the Raman spectroscopic results and suggests a possible mechanism of unzipping determined by combined effects of the structural characteristics of SWNTs and applied field.
Herein, we report the emergence of multicolor photoluminescence in a mixed-valence manganite nanoparticle La0.67Sr0.33MnO3 (LSMO NP) achieved through electronic structural modification of the nanoparticles upon functionalization with a biocompatible organic ligand, sodium tartrate. From UV–vis absorption, X-ray photoelectron spectroscopy (XPS), time-resolved photoluminescence study, and Raman spectroscopic measurements, it is revealed that ligand-to-metal charge transfer transitions from highest occupied molecular orbital (HOMO, centered in tartrate ligand) to lowest unoccupied molecular orbital (LUMO, centered in Mn3+/4+ of the NPs), and d–d transitions involving Jahn–Teller sensitive Mn3+ ions in the NPs plays the central role behind the origin of multiple photoluminescence from the ligand functionalized LSMO NPs.
Resistive random access memory (RRAM) is the most promising candidate for next generation nonvolatile memory. In this article, resistive switching in PdO thin fi lm is investigated. The fabricated in-plane devices showed voltage pulse induced multilevel resistive switching (MRS) with as many as fi ve states under ambient conditions with high degrees of retention and endurance. The I -V characteristics of the different memory states are linear and only a small reading voltage (≈10 mV) is necessary. Raman mapping of PdO (B 1g mode, 650 cm -1 ) and temperature-dependent electrical transport measurements provide an insight into possible redox mechanism involving PdO/Pd particles. For the fi rst time, the switching effi ciency of a MRS device is uniquely defi ned in terms of a parameter called "multiplex number ( M )," which is the sum of the total number of memory states and the ratio between the number of switching events observed in a device and the total number of possible switching events. The present PdO MRS device exhibits the highest M value compared to the values evaluated from the literature examples. Such high performance MRS in PdO devices makes them potential candidates for RRAM and neuromorphic circuit applications.
Magnetorheological fluids have numerous engineering applications due to their interesting field assisted rheological behavior. Most commonly used dispersed phase in MR fluids is carbonyl iron (CI). The relatively high cost of CI warrants the need to develop cheaper alternatives to CI, without compromising rheological properties. With the above goal in mind, we have synthesized sodium sulphonate capped electrolytic iron based MR fluid and studied their magnetorheological properties. The results are compared with that of CI based MR fluid. EI and CI particles of average particle size of ∼10 μm with fumed silica particles additives are used in the present study. The dynamic yield stress for EI and CI based MR fluid were found to vary with field strength with an exponent of roughly 1.2 and 1.24, respectively. The slightly lower static and dynamic yield stress values of EI based MR fluid is attributed to the lower magnetization and polydispersity values. The dynamic yield stress showed a decrease of 18.73% and 61.8% for field strengths of 177 mT and 531 mT, respectively as the temperature was increased from 293 to 323 K. The optorheological studies showed a peak in the loss moduli, close to the crossover point of the storage and loss moduli, due to freely moving large sized aggregates along the shear direction that are dislodged from the rheometer plates at higher strains. Our results suggests that EI based MR fluids have magnetorheological behavior comparable to that of CI based MR fluids. As EI is much cheaper than CI, our findings will have important commercial implications in producing cost effective EI based MR fluids.
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