Ramakrishna Podila

Effects of layer stacking on the combination raman modes in graphene

We have observed new combination modes in the range from 1650 to 2300 cm(-1) in single-(SLG), bi-, few-layer and incommensurate bilayer graphene (IBLG) on silicon dioxide substrates. A peak at ∼1860 cm(-1) (iTALO-) is observed due to a combination of the in-plane transverse acoustic (iTA) and the longitudinal optical (LO) phonons. The intensity of this peak decreases with increasing number of layers and this peak is absent for bulk graphite. The overtone of the out-of-plane transverse optical (oTO) phonon at ∼1750 cm(-1), also called the M band, is suppressed for both SLG and IBLG. In addition, two previously unidentified modes at ∼2200 and ∼1880 cm(-1) are observed in SLG. The 2220 cm(-1) (1880 cm(-1)) mode is tentatively assigned to the combination mode of in-plane transverse optical (iTO) and TA phonons (oTO+LO phonons) around the K point in the graphene Brillouin zone. Finally, the peak frequency of the 1880 (2220) cm(-1) mode is observed to increase (decrease) linearly with increasing graphene layers.

Silver Nanoparticle Protein Corona Composition in Cell Culture Media

The potential applications of nanomaterials as drug delivery systems and in other products continue to expand. Upon introduction into physiological environments and driven by energetics, nanomaterials readily associate proteins forming a protein corona (PC) on their surface. This PC influences the nanomaterial’s surface characteristics and may impact their interaction with cells. To determine the biological impact of nanomaterial exposure as well as nanotherapeutic applications, it is necessary to understand PC formation. Utilizing a label-free mass spectrometry-based proteomics approach, we examined the composition of the PC for a set of four silver nanoparticles (AgNPs) including citrate-stabilized and polyvinlypyrrolidone-stabilized (PVP) colloidal silver (20 or 110 nm diameter). To simulate cell culture conditions, AgNPs were incubated for 1 h in Dulbecco’s Modified Eagle Medium supplemented with 10% fetal bovine serum, washed, coronal proteins solubilized, and proteins identified and quantified by label-free LC-MS/MS. To determine which attributes influence PC formation, the AgNPs were characterized in both water and cell culture media with 10% FBS. All AgNPs associated a common subset of 11 proteins including albumin, apolipoproteins, keratins, and other serum proteins. 110 nm citrate- and PVP-stabilized AgNPs were found to bind the greatest number of proteins (79 and 85 respectively) compared to 20 nm citrate- and PVP-stabilized AgNPs (45 and 48 respectively), suggesting a difference in PC formation based on surface curvature. While no relationships were found for other protein parameters (isoelectric point or aliphatic index), the PC on 20 nm AgNPs (PVP and citrate) consisted of more hydrophobic proteins compared to 110 nm AgNPs implying that this class of proteins are more receptive to curvature-induced folding and crowding in exchange for an increased hydration in the aqueous environment. These observations demonstrate the significance of electrostatic and hydrophobic interactions in the formation of the PC which may have broad biological and toxicological implications.

Nanobiotechnology can boost crop production and quality: first evidence from increased plant biomass, fruit yield and phytomedicine content in bitter melon (Momordica charantia)

BackgroundRecent research on nanoparticles in a number of crops has evidenced for enhanced germination and seedling growth, physiological activities including photosynthetic activity and nitrogen metabolism, mRNA expression and protein level, and also positive changes in gene expression indicating their potential use in crop improvement. We used a medicinally rich vegetable crop, bitter melon, as a model to evaluate the effects of seed treatment with a carbon-based nanoparticle, fullerol [C60(OH)20], on yield of plant biomass and fruit characters, and phytomedicine contents in fruits.ResultsWe confirmed the uptake, translocation and accumulation of fullerol through bright field imaging and Fourier transform infra-red spectroscopy. We observed varied effects of seed treatment at five concentrations, including non-consequential and positive, on plant biomass yield, fruit yield and its component characters, and content of five phytomedicines in fruits. Fullerol-treatment resulted in increases up to 54% in biomass yield and 24% in water content. Increases of up to 20% in fruit length, 59% in fruit number, and 70% in fruit weight led to an improvement up to 128% in fruit yield. Contents of two anticancer phytomedicines, cucurbitacin-B and lycopene, were enhanced up to 74% and 82%, respectively, and contents of two antidiabetic phytomedicines, charantin and insulin, were augmented up to 20% and 91%, respectively. Non-significant correlation inter se plant biomass, fruit yield, phytomedicine content and water content evidenced for separate genetic control and biosynthetic pathways for production of plant biomass, fruits, and phytomedicines in fruits, and also no impact of increased water uptake.ConclusionsWhile our results indicated possibility of improving crop yield and quality by using proper concentrations of fullerol, extreme caution needs to be exercised given emerging knowledge about accumulation and toxicity of nanoparticles in bodily tissues.

Multi-walled carbon nanotube instillation impairs pulmonary function in C57BL/6 mice

BackgroundMulti-walled carbon nanotubes (MWCNTs) are widely used in many disciplines due to their unique physical and chemical properties. Therefore, some concerns about the possible human health and environmental impacts of manufactured MWCNTs are rising. We hypothesized that instillation of MWCNTs impairs pulmonary function in C57BL/6 mice due to development of lung inflammation and fibrosis.MethodsMWCNTs were administered to C57BL/6 mice by oropharyngeal aspiration (1, 2, and 4 mg/kg) and we assessed lung inflammation and fibrosis by inflammatory cell infiltration, collagen content, and histological assessment. Pulmonary function was assessed using a FlexiVent system and levels of Ccl3, Ccl11, Mmp13 and IL-33 were measured by RT-PCR and ELISA.ResultsMice administered MWCNTs exhibited increased inflammatory cell infiltration, collagen deposition and granuloma formation in lung tissue, which correlated with impaired pulmonary function as assessed by increased resistance, tissue damping, and decreased lung compliance. Pulmonary exposure to MWCNTs induced an inflammatory signature marked by cytokine (IL-33), chemokine (Ccl3 and Ccl11), and protease production (Mmp13) that promoted the inflammatory and fibrotic changes observed within the lung.ConclusionsThese results further highlight the potential adverse health effects that may occur following MWCNT exposure and therefore we suggest these materials may pose a significant risk leading to impaired lung function following environmental and occupational exposures.

Origin of FM Ordering in Pristine Micro- and Nanostructured ZnO

An unexpected presence of ferromagnetic (FM) ordering in nanostructured nonmagnetic metal oxides has been reported previously. Though this property was attributed to the presence of defects, systematic experimental and theoretical studies to pinpoint its origin and mechanism are lacking. While it is widely believed that oxygen vacancies are responsible for FM ordering, surprisingly we find that annealing as-prepared samples at low temperature (high temperature) in flowing oxygen actually enhances (diminishes) the FM ordering. For these reasons, we have prepared, annealed in different environments, and measured the ensuing magnetization in micrometer and nanoscale ZnO with varying crystallinity. We further find from our magnetization measurements and ab initio calculations that a range of magnetic properties in ZnO can result, depending on the sample preparation and annealing conditions. For example, within the same ZnO sample we have observed ferro- to para- and diamagnetic responses depending on the annealing conditions. We also explored the effects of surface states on the magnetic behavior of nanoscale ZnO through detailed calculations.

Defect-Engineered Graphene for High-Energy- and High-Power-Density Supercapacitor Devices

Defects are often written off as performance limiters. Contrary to this notion, it is shown that controlling the defect configuration in graphene is critical to overcome a fundamental limitation posed by quantum capacitance and opens new channels for ion diffusion. Defect-engineered graphene flexible pouch capacitors with energy densities of 500% higher than the state-of-the-art supercapacitors are demonstrated.The development of high-energy and high-power density supercapacitors (SCs) is critical for enabling next-generation energy storage applications. Nanocarbons are excellent SC electrode materials due to their economic viability, high-surface area, and high stability. Although nanocarbons have high theoretical surface area and hence high double layer capacitance, the net amount of energy stored in nanocarbon-SCs is much below theoretical limits due to two inherent bottlenecks: i) their low quantum capacitance and ii) limited ion-accessible surface area. Here, we demonstrate that defects in graphene could be effectively used to mitigate these bottlenecks by drastically increasing the quantum capacitance and opening new channels to facilitate ion diffusion in otherwise closed interlayer spaces. Our results support the emergence of a new energy paradigm in SCs with 250% enhancement in double layer capacitance beyond the theoretical limit. Furthermore, we demonstrate prototype defect engineered bulk SC devices with energy densities 500% higher than state-of-the-art commercial SCs without compromising the power density.

Toxicity of Engineered Nanomaterials: A Physicochemical Perspective

The global market for nanomaterial‐based products is forecasted to reach 100 billion dollars per annum for 2011–2015. Extensive manufacturing and the use of engineered nanomaterials have raised concerns regarding their impact on biological response in living organisms and the environment at large. The fundamental properties of nanomaterials exhibit a complex dependence upon several factors such as their morphology, size, defects, and chemical stability. Therefore, it is exceedingly difficult to correlate their biological response with their intricate physicochemical properties. For example, varying toxic response may ensue due to different methods of nanomaterial preparation, dissimilar impurities, and defects. In this review, we surveyed the existing literature on the dependence of cytotoxicity on physicochemical properties. We found that ENM size, shape, defect density, physicochemical stability, and surface modification to be the main causes that elicit altered physiological response or cytotoxicity.

Effects of surface functional groups on the formation of nanoparticle-protein corona.

Herein, we examined the dependence of protein adsorption on the nanoparticle surface in the presence of functional groups. Our UV-visible spectrophotometry, transmission electron microscopy, infrared spectroscopy, and dynamic light scattering measurements evidently suggested that the functional groups play an important role in the formation of nanoparticle-protein corona. We found that uncoated and surfactant-free silver nanoparticles derived from a laser ablation process promoted a maximum protein (bovine serum albumin) coating due to increased changes in entropy. On the other hand, bovine serum albumin displayed a relatively lower affinity for electrostatically stabilized nanoparticles due to the constrained entropy changes.

Formation of a Protein Corona on Silver Nanoparticles Mediates Cellular Toxicity via Scavenger Receptors

Addition of a protein corona (PC) or protein adsorption layer on the surface of nanomaterials following their introduction into physiological environments may modify their activity, bio-distribution, cellular uptake, clearance, and toxicity. We hypothesize that silver nanoparticles (AgNPs) will associate with proteins common to human serum and cell culture media forming a PC that will impact cell activation and cytotoxicity. Furthermore, the role of scavenger receptor BI (SR-BI) in mediating this toxicity was evaluated. Citrate-suspended 20 nm AgNPs were incubated with human serum albumin (HSA), bovine serum albumin (BSA), high-density lipoprotein (HDL), or water (control) to form a PC. AgNPs associated with each protein (HSA, BSA, and HDL) forming PCs as assessed by electron microscopy, hyperspectral analysis, ζ-potential, and hydrodynamic size. Addition of the PC decreased uptake of AgNPs by rat lung epithelial and rat aortic endothelial cells. Hyperspectral analysis demonstrated a loss of the AgNP PC following internalization. Cells demonstrated concentration-dependent cytotoxicity following exposure to AgNPs with or without PCs (0, 6.25, 12.5, 25 or 50 μg/ml). All PC-coated AgNPs were found to activate cells by inducing IL-6 mRNA expression. A small molecule SR-BI inhibitor was utilized to determine the role of SR-BI in the observed effects. Pretreatment with the SR-BI inhibitor decreased internalization of AgNPs with or without PCs, and reduced both cytotoxicity and IL-6 mRNA expression. This study characterizes the formation of a PC on AgNPs and demonstrates its influence on cytotoxicity and cell activation through a cell surface receptor.

Preferential Scattering by Interfacial Charged Defects for Enhanced Thermoelectric Performance in Few-layered n-type Bi2Te3

Over the past two decades several nano-structuring methods have helped improve the figure of merit (ZT) in the state-of-the art bulk thermoelectric materials. While these methods could enhance the thermoelectric performance of p-type Bi2Te3, it was frustrating to researchers that they proved ineffective for n-type Bi2Te3 due to the inevitable deterioration of its thermoelectric properties in the basal plane. Here, we describe a novel chemical-exfoliation spark-plasma-sintering (CE-SPS) nano-structuring process, which transforms the microstructure of n-type Bi2Te3 in an extraordinary manner without compromising its basal plane properties. The CE-SPS processing leads to preferential scattering of electrons at charged grain boundaries, and thereby increases the electrical conductivity despite the presence of numerous grain boundaries, and mitigates the bipolar effect via band occupancy optimization leading to an upshift (by ~ 100 K) and stabilization of the ZT peak over a broad temperature range of ~ 150 K.