Optically transparent polymer devices for in situ assessment of cell electroporation

In order to study cell electroporation in situ, polymer devices have been fabricated from poly-dimethyl siloxane with transparent indium tin oxide parallel plate electrodes in horizontal geometry. This geometry with cells located on a single focal plane at the interface of the bottom electrode allows a longer observation time in both transmitted bright-field and reflected fluorescence microscopy modes. Using propidium iodide (PI) as a marker dye, the number of electroporated cells in a typical culture volume of 10-100 mu l was quantified in situ as a function of applied voltage from 10 to 90 V in a series of 2-ms pulses across 0.5-mm electrode spacing. The electric field at the interface and device current was calculated using a model that takes into account bulk screening of the transient pulse. The voltage dependence of the number of electroporated cells could be explained using a stochastic model for the electroporation kinetics, and the free energy for pore formation was found to be kT at room temperature. With this device, the optimum electroporation conditions can be quickly determined by monitoring the uptake of PI marker dye in situ under the application of millisecond voltage pulses. The electroporation efficiency was also quantified using an ex situ fluorescence-assisted cell sorter, and the morphology of cultured cells was evaluated after the pulsing experiment. Importantly, the efficacy of the developed device was tested independently using two cell lines (C2C12 mouse myoblast cells and yeast cells) as well as in three different electroporation buffers (phosphate buffer saline, electroporation buffer and 10 % glycerol).

Low-Wear High-Friction Behavior of Copper Matrix Composites Dispersed With an In Situ Polymer Derived Ceramic

We show that copper-matrix composites that contain 20 vol. % of an in situ processed, polymer-derived, ceramic phase constituted from Si-C-N have unusual friction-and-wear properties. They show negligible wear despite a coefficient of friction (COF) that approaches 0.7. This behavior is ascribed to the lamellar structure of the composite such that the interlamellar regions are infused with nanoscale dispersion of ceramic particles. There is significant hardening of the composite just adjacent to the wear surface by severe plastic deformation.

Rapid reduction of GO by hydrogen spill-over mechanism by in situ generated nanoparticles at room temperature and their catalytic performance towards 4-nitrophenol reduction and ethanol oxidation

Here, we report the clean and facile synthesis of Pt and Pd nanoparticles decorated on reduced graphene oxide (rGO) by the simultaneous reduction of graphene oxide (GO) and the metal ions in Mg/acid medium. As-generated Pt and Pd nanoparticles serve as a heterogeneous catalyst for the further reduction of the rGO by the hydrogen spill-over process. The C/O ratio is much higher as compared to the rGO obtained by the reduction of GO by only Mg/acid. Overall, the process is rapid, facile and green that does not require any toxic chemical agent or any rigorous chemical reactions. We perform the catalytic reduction of 4-nitophenol (4-NP) to 4-aminophenol (4-AP) at room temperature by Pd@rGO and Pt@rGO. The reduction is complete within 35 s for Pd@rGO and 60 s for Pt@rGO when 50 mu g of hybrid catalyst is used for 0.5 ml of 1 mM of 4-NP. In case of ethanol oxidation, the current density for Pd@rGO is comparable to commercial Pt/C but is doubled for Pt@rGO. Overall, both structures show highly stable catalytic activity compared to commercial Pt/C. (C) 2014 Elsevier B.V. All rights reserved.

A critical review on in situ reduction of graphene oxide during preparation of conducting polymeric nanocomposites

Graphene oxide (GO), prepared by chemical oxidation of graphite, serves as a building block for developing polymeric nanocomposites. However, their application in electrical conductivity is limited by the fact that the oxygen sites on GO trap electrons and impede charge transport. Conducting nanocomposites can be developed by reducing GO. Various strategies have been adopted to either reduce GO ex situ, before the composite preparation, or in situ during the development of the nanocomposites. The current state of research on in situ reduction of GO during the preparation of conducting polymeric nanocomposites is discussed in this review. The mechanism and the efficiency of reduction is discussed with respect to various strategies employed during the preparation of the nanocomposite, the type of polymer used, and the processing conditions employed, etc. Its overall effect on the electrical conductivity of the nanocomposites is also discussed and the future outlook in this area is presented.

A Mild Protocol for the Regioselective Ring Opening of Doubly Activated Cyclopropanes by Using Selenolates Generated in Situ: Synthesis of Functionalized Organoselenium Compounds

A variety of functionalized organoselenium compounds were synthesized from doubly activated cyclopropanes and diselenides in the presence of sodium borohydride. A range of substituents were stable under these reaction conditions. Additionally, we extended the scope of the method by reducing nitro groups in the products to give the corresponding selenium-containing unnatural amino acids.

RNA nucleosides as chiral sensing agents in NMR spectroscopy

The study reports chiral sensing properties of RNA nucleosides. Adenosine, guanosine, uridine and cytidine are used as chiral derivatizing agents to differentiate chiral 1 degrees-amines. A three component protocol has been adopted for complexation of nucleosides and amines. The chiral differentiating ability of nucleosides is examined for different amines based on the H-1 NMR chemical shift differences of diastereomers (Delta delta(R,S)). Enantiomeric differentiation has been observed at multiple chemically distinct proton sites. Adenosine and guanosine exhibit large chiral differentiation (Delta delta(R,S)) due to the presence of a purine ring. The diastereomeric excess (de) measured by using adenosine is in good agreement with the gravimetric values.

In-situ synthesized poly(vinyl butyral)/MMT-clay nanocomposites: The role of degree of acetalization and clay content on thermal, mechanical and permeability properties of PVB matrix

Poly(vinyl butyral) - MMT clay nanocomposites were synthesized in situ with three different degrees of acetalization and with varying clay content for each vinyl butyral polymer ratio. The clay nano-platelet galleries were expanded, as determined by X-ray diffraction and TEM analysis. The glass transition temperature of the polymer nanocomposites were found to be similar to 56 degrees C and similar to 52 degrees C for the neat polymer and the 4% clay loaded samples, respectively. The 4 wt% clay loaded film showed higher strength and low strain to failure. The dynamic mechanical analysis also confirmed the improved stability of the matrix. The matrix with 0.5 butyral to alcohol ratio for 4 wt% clay exhibited good water vapor transmission compared to all other compositions. The encapsulated devices with 2.5 and 4 wt% clay loaded films increases the device life time and the efficiencies of these films were 50% higher than their encapsulated pristine polymer films. (C) 2015 Elsevier Ltd. All rights reserved.

In Situ Crystallographic Probing on Ameliorating Effect of Sulfide Additives and Carbon Grafting in Iron Electrodes

Beneficial effects of carbon grafting into the iron active material for rechargeable alkaline-iron-electrodes with and without Bi2S3 additive is probed by in situ X-ray diffraction in conjunction with Extended X-ray Absorption Fine Structure (EXAFS) and electrochemistry. EXAFS data unravel that the composition of pristine active material (PAM) for iron electrodes comprises 87% of magnetite and 13% of alpha-iron while carbon-grafted active material comprises 60% of magnetite and 40% of alpha-iron. In situ XRD patterns are recorded using a specially designed electrochemical cell. XRD data reflect that magnetite present in PAM iron electrode, without bismuth sulfide additive, is not reduced during charging while PAM iron electrode with bismuth sulfide additive is partially reduced to alpha-Fe/Fe(OH)(2). Interestingly, carbon-grafted-iron electrodes with bismuth sulfide exhibit complete conversion of active material to alpha-Fe/Fe(OH)2. The ameliorating effect of carbon grafting is substantiated by kinetic parameters obtained from steady-state potentiostatic polarization and Tafel plots. The mechanism for iron-electrode charge - discharge reactions are discussed in the light of the potential - pH diagrams for Fe - H2O, S - H2O and FeSads - H2O systems and it is surmised that carbon grafting into iron active material promotes its electrochemical utilization. (C) The Author(s) 2015. Published by ECS. All rights reserved.

A novel in-situ polymer derived nano ceramic MMC by friction stir processing

Fiction stir processing (FSP) is a solid state technique used for material processing. Tool wear and the agglomeration of ceramic particles have been serious issues in FSP of metal matrix composites. In the present study, FSP has been employed to disperse the nanoscale particles of a polymer-derived silicon carbonitride (SiCN) ceramic phase into copper by an in-situ process. SiCN cross linked polymer particles were incorporated using multi-pass ESP into pure copper to form bulk particulate metal matrix composites. The polymer was then converted into ceramic through an in-situ pyrolysis process and dispersed by ESP. Multi-pass processing was carried out to remove porosity from the samples and also for the uniform dispersion of polymer derived ceramic particles. Microstructural observations were carried out using Field Emission Scanning Electron Microscopy (FE-SEM) and Transmission Electron Microscopy (TEM) of the composite. The results indicate a uniform distribution of similar to 100 nm size particles of the ceramic phase in the copper matrix after ESP. The nanocomposite exhibits a five fold increase in microhardness (260HV(100)) which is attributed to the nano scale dispersion of ceramic particles. A mechanism has been proposed for the fracturing of PDC particles during multi pass FSP. (C) 2015 Elsevier Ltd. All rights reserved

Hydrogelation of bile acid-peptide conjugates and in situ synthesis of silver and gold nanoparticles in the hydrogel matrix

Fabricating supramolecular hydrogels with embedded metal nanostructures is important for the design of novel hybrid nanocomposite materials for diverse applications such as biosensing and chemosensing platforms, catalytic and antibacterial functional materials etc. Supramolecular self-assembly of bile acid-dipeptide conjugates has led to the formation of new supramolecular hydrogels. Gelation of these molecules depends strongly on the hydrophobic character of the bile acids. The possibility of in situ fabrication of Ag and Au NPs in these supramolecular hydrogels by incorporating Ag+ and Au3+ salts was investigated via photoreduction. Chemical reductions of Ag+ and Au3+ salts in the hydrogels were performed without adding any external stabilizing agents. In this report we have shown that the color, size and shape of silver nanoparticles formed by photoreduction depend on the amino acid residue of the side chain.

Quantitative In Situ Analysis of Deformation in Sliding Metals: Effect of Initial Strain State

Using in situ, high-speed imaging of a hard wedge sliding against pure aluminum, and image analysis by particle image velocimetry, the deformation field in sliding is mapped at high resolution. This model system is representative of asperity contacts on engineered surfaces and die-workpiece contacts in deformation and machining processes. It is shown that large, uniform plastic strains of 1-5 can be imposed at the Al surface, up to depths of 500 mu m, under suitable sliding conditions. The spatial strain and strain rate distributions are significantly influenced by the initial deformation state of the Al, e.g., extent of work hardening, and sliding incidence angle. Uniform straining occurs only under conditions of steady laminar flow in the metal. Large pre-strains and higher sliding angles promote breakdown in laminar flow due to surface fold formation or flow localization in the form of shear bands, thus imposing limits on uniform straining by sliding. Avoidance of unsteady sliding conditions, and selection of parameters like sliding angle, thus provides a way to control the deformation field. Key characteristics of the sliding deformation such as strain and strain rate, laminar flow, folding and prow formation are well predicted by finite element simulation. The deformation field provides a quantitative basis for interpreting wear particle formation. Implications for engineering functionally graded surfaces, sliding wear and ductile failure in metals are discussed.

In-situ study of microscale fracture of diffusion aluminide bond coats: Effect of platinum

The influence of Pt layer thickness on the fracture behavior of PtNiAl bond coats was studied in situ using clamped micro-beam bend tests inside a scanning electron microscope (SEM). Clamped beam bending is a fairly well established micro-scale fracture test geometry that has been previously used in determination of fracture toughness of Si and PtNiAl bond coats. The increasing amount of Pt in the bond coat matrix was accompanied by several other microstructural changes such as an increase in the volume fraction of alpha-Cr precipitate particles in the coating as well as a marginal decrease in the grain size of the matrix. In addition, Pt alters the defect chemistry of the B2-NiAl structure, directly affecting its elastic properties. A strong correlation was found between the fracture toughness and the initial Pt layer thickness associated with the bond coat. As the Pt layer thickness was increased from 0 to 5 mu m, resulting in increasing Pt concentration from 0 to 14.2 at.% in the B2-NiAl matrix and changing alpha-Cr precipitate fraction, the initiation fracture toughness (K-IC) was seen to rise from 6.4 to 8.5 MPa.m(1/2). R-curve behavior was observed in these coatings, with K-IC doubling for a crack propagation length of 2.5 mu m. The reasons for the toughening are analyzed to be a combination of material's microstructure (crack kinking and bridging due to the precipitates) as well as size effects, as the crack approaches closer to the free surface in a micro-scale sample.

Rapid synthesis of hybrids and hollow PdO nanostructures by controlled in situ dissolution of a ZnO nanorod template: insights into the formation mechanism and thermal stability

Hollow nanomaterials have attracted a lot of interest by virtue of their wide range of applications that arise primarily due to their unique architecture. A common strategy to synthesize hollow nanomaterials is by nucleation of the shell material over a preformed core and subsequent dissolution of the core in the second step. Herein an ultrafast, microwave route has been demonstrated, to synthesize PdO nanotubes in a single step using ZnO as a sacrificial template. The mechanism of the nanotube formation has been investigated in detail using control experiments. By tuning the starting ratio of PdCl2 : ZnO, hollow to hybrid PdO nanostructures could be obtained using the same method. Conversion of the PdO to Pd nanotubes has been shown by simple NaBH4 treatment. The thermal stability of the PdO nanotubes has been studied. The insights presented here are general and applicable for the synthesis of hybrids/hollow structures in other systems as well.

In-situ flexural OPV measurements on flexible glass substrate

In-situ dark and light IV characteristics of inverted P3HT-PCBM devices on flexible glass substrates were measured while bending. Bending set up was simple and home built with servo controlled 2 parallel plate movements. ITO was sputter coated onto the thin flexible glass sheets of 25mmx25mm size in the lab. OPV devices were fabricated inside the glove box and conversion efficiency measured was about 2.8%. Bending of the device substrates and simultaneous PV measurements were carried out in ambient conditions. It was observed that the J(SC) and efficiency increased until the substrate breaking point but the V-OC and fill factor remained unchanged.

In Situ NMR Insights into the Electrochemical Reaction of Cu3P Electrodes in Lithium Batteries

This study reports a multinuclei in situ (real-time) NMR spectroscopic characterization of the electrochemical reactions of a negative Cu3P electrode toward lithium. Taking advantage of the different nuclear spin characteristics, we have obtained real-time P-31 and Li-7 NMR data for a comprehensive understanding of the electrochemical mechanism during the discharge and charge processes of a lithium battery. The large NMR chemical shift span of P-31 facilitates the observation of the chemical evolutions of different lithiated and delithiated LixCu3-xP phases, whereas the quadrupolar line features in Li-7 enable identification of asymmetric Li sites. These combined NMR data offer an unambiguous identification of four distinct LixCu3-xP phases, Cu3P, Li0.2Cu2.8P, Li2CuP, and. Li3P, and the characterization of their involvement in the electrochemical reactions. The NMR data led us to propose a delithiation process involving the intercalation of metallic Cu-0 atomic aggregates into the Li2CuP structure to form a Cu-0-Li2-xCu1-xP phase. This process might be responsible for the poor capacity retention in Cu3P lithium batteries when cycled to a low voltage.