Micromechanical properties of carbon nitride films deposited by radio-frequency-assisted filtered cathodic vacuum arc

Super-hard and elastic carbon nitride films have been synthesized by using an off-plane double-bend filtered cathodic vacuum arc combined with a radio-frequency nitrogen-ion beam source. A nanoindenter was used to determine the micromechanical properties of the deposited films. X-ray photoelectron spectroscopy was used to study the composition and bonding structure of the deposited films. The influence of nitrogen ion energy on the structure and micromechanical properties of the deposited films was systematically studied. As the nitrogen ion energy is increased, the microhardness, Young’s modulus and elastic recovery also increase, reaching a maximum of 47 GPa, 400 GPa, and 87.5%, respectively, at a nitrogen ion energy of 100 eV. Further increase in nitrogen ion energy results in a decrease in microhardness, Young’s modulus and elastic recovery of the deposited films. The formation of five-membered rings, as indicated by XPS, which causes bending of the basal planes and forms a three-dimensional rigid covalent bond network, contributes to the super-hardness, Young’ s modulus and high elastic recovery of the films deposited at a nitrogen ion energy of 100 eV. Revised version: 29 October 2001 / Accepted: 7 November 2001 / Published online: 2 May 2002     

Synthetic Modulation of an Unstable Dehydrosecodine-type Intermediate and Its Encapsulation into a Confined Cavity Enable Its X-ray Crystallographic Observation

Numerous indole alkaloids such as the iboga- and aspidosperma-type are believed to be biosynthesized via a common hypothetical intermediate, dehydrosecodine. The highly reactive nature of dehydrosecodine-type compounds has hampered their isolation and structural elucidation. In this study, we achieved the first X-ray structural determination of a dehydrosecodine-type compound by integrating synthetic optimization of the reactivity and stabilizing the fragile molecule by encapsulation into a supramolecular host. Formation of a 1 : 1 complex of the dehydrosecodine-type labile guest bearing both vinyl indole and dihydropyridine units with the host was observed. This integrated approach not only provides insights into the biosynthetic conversions but also allows stabilization and storage of the reactive and otherwise short-lived intermediate within the confined hydrophobic cavity.     

Temporal phase retrieval from a complex field in digital holographic interferometry

We describe a novel method of processing complex phasors in digital holographic interferometry (DHI). Unlike the commonly used digital phase subtraction method that operates on the phase itself, the proposed method operates on the complex phasor instead. Two temporal phase retrieval algorithms are developed in which the complex phasor of each pixel is measured and analyzed as a function of time. The developed algorithms are demonstrated in profile measurement of step heights. Experimental results show that the proposed phase retrieval algorithms for DHI perform well compared with conventional methods.     

Evaluation of chemical labeling strategies for monitoring HCV RNA using vibrational microscopy

Raman and coherent anti-Stokes Raman scattering (CARS) microscopies have the potential to aid in detailed longitudinal studies of RNA localization. Here, we evaluate the use of carbon-deuterium and benzonitrile functional group labels as contrast agents for vibrational imaging of hepatitis C virus (HCV) replicon RNA. Dynamic light scattering and atomic force microscopy were used to evaluate the structural consequences of altering HCV subgenomic replicon RNA. Modification with benzonitrile labels caused the replicon RNA tertiary structure to partially unfold. Conversely, deuterium-modified replicon RNA was structurally similar to unmodified replicon RNA. Furthermore, the deuterated replicon RNA provided promising vibrational contrast in Raman imaging experiments. The functional effect of modifying subgenomic HCV replicon RNA was evaluated using the luciferase gene as a genetic reporter of translation. Benzonitrile labeling of the replicon RNA prevented translation in cell-based luciferase assays, while the deuterated replicon RNA retained both translation and replication competency. Thus, while the scattering cross-section for benzonitrile labels was higher, only carbon-deuterium labels proved to be non-perturbative to the function of HCV replicon RNA.     

A Glycosylated Cationic Block Poly(β-peptide) Reverses Intrinsic Antibiotic Resistance in All ESKAPE Gram-Negative Bacteria

Carbapenem-resistant Gram-negative bacteria (GNB) are heading the list of pathogens for which antibiotics are the most critically needed. Many antibiotics are either unable to penetrate the outer-membrane or are excluded by efflux mechanisms. Here, we report a cationic block β-peptide (PAS8-b-PDM12) that reverses intrinsic antibiotic resistance in GNB by two distinct mechanisms of action. PAS8-b-PDM12 does not only compromise the integrity of the bacterial outer-membrane, it also deactivates efflux pump systems by dissipating the transmembrane electrochemical potential. As a result, PAS8-b-PDM12 sensitizes carbapenem- and colistin-resistant GNB to multiple antibiotics in vitro and in vivo. The β-peptide allows the perfect alternation of cationic versus hydrophobic side chains, representing a significant improvement over previous antimicrobial α-peptides sensitizing agents. Together, our results indicate that it is technically possible for a single adjuvant to reverse innate antibiotic resistance in all pathogenic GNB of the ESKAPE group, including those resistant to last resort antibiotics.     

Investigation of final-stage sintering of various microsize structures prepared by micro powder injection molding

Micro powder injection molding (μPIM) has been developed as a potential technique for mass production of microcomponents in microsystems due to its shaping complexity at low cost, in which sintering is a crucial step to dictate the final properties of the microcomponents. In this paper, final-stage sintering behavior of 316L stainless steel microsize structures prepared by μPIM, φ100 μm and φ60 μm, respectively, was studied. The effect of size reduction in the regime of micrometers on the density of various microsize structures was investigated. Sintering kinetics of the microsize structures of φ100 μm and φ60 μm were studied based on particle level sintering models. It is found that the microsize structures of φ60 μm had higher density than the microsize structures of φ100 μm given the same sintering condition. The results indicate that size reduction in the regime of micrometers facilitated densification of microsize structures. The grain growth mechanism of microsize structures varied with size. Whereas the grain growth of the microsize structures of φ100 μm is governed by surface-diffusion-controlled pore drag, the grain growth of the microsize structures of φ60 μm is controlled by boundary diffusion. During densification, the microsize structures, φ100 μm and φ60 μm, are both controlled by lattice diffusion. The corresponding activation energies are reported in the paper.     

Deuterated dimethyl sulfoxide as a good NMR solvent for the characterization of alkali metal cyclopentadienides, amides, alkoxides and phenoxides

A series of alkali metal cyclopentadienides, amides, alkoxides and phenoxides was characterized using NMR spectroscopy in deuterated dimethyl sulfoxide. Deuterated dimethyl sulfoxide showed very good stability and solubility for these compounds. Very nice and well resolved spectra were obtained for most compounds tested. The low cost of the solvent makes it possible to use it for the routine characterization of these alkali salts as the ligands in organometallic synthesis.     

Three-stage transformation pathway from nanodiamonds to fullerenes

The dynamics of structure evolution of nanodiamonds ranging from 22 to 318 atoms of various shapes is studied by density functional tight-binding molecular dynamics. The spherical and cubic nanodiamonds can be transformed into fullerene-like structures upon heating. A number of the transformed fullerenes consist of pentagons and hexagons only. Others contain squares, heptagons, and octagons. One simulated fullerene is an isomer of C(60). The temperature of the transformation depends on the size, shape, and orientation of initial cluster. To be transformed into onion-like fullerenes, the spherical nanodiamonds should have 200 atoms or more, while the cubic ones require 302 atoms or more. The time-resolved energy profiles of all the transformations clearly reveal three-stage transformation character. During the first stage, the energy reduces quickly due to converting sp(3) carbon with dangling bond at the surface into sp(2) one, and the formation of partial sp(2) envelope wrapping the cluster. For the second stage, energy decreases slowly. The remaining interior carbon atoms come to the surface through the hole in the sp(2) envelope, and similar amount of sp(3) and sp(2) atoms coexist. The third stage involves the closure of holes, accompanied by the detachment of C(2) molecules and carbon chains from the edges. The energy decreases relatively fast in this stage. The proposed three-stage transformation pathway holds for all the simulations performed in this work, including those with the instant heating.     

Carbon-bonded silver nanoparticles: alkyne-functionalized ligands for SERS imaging of mammalian cells

Silver nanoparticles bonded to terminal alkynes form stable particles in aqueous solution, produce strong SERS signals for molecular imaging that arise from the carbon-metal bond, and expand the scope of molecules that can be used to stably functionalize plasmonic particles for mammalian cell imaging applications. β-Lactams represent a class of biologically important molecules that can be adapted to SERS studies in this manner.     

Nanostructured PdRu/C catalysts for formic acid oxidation

Pd and bimetallic PdRu nanoparticles supported on Vulcan XC-72 carbon prepared by the microwave-assisted polyol process are examined as electrocatalysts for the electrooxidation of formic acid. The catalysts are characterized by transmission electron microscopy and X-ray diffraction. The Pd and PdRu nanoparticles with sizes of <10 nm display the characteristic diffraction peaks of a Pd face-centered cubic (fcc) crystal structure. It is found that the addition of Ru to Pd/C can decrease the lattice parameter of Pd (fcc) crystal. The electrocatalytic activities of the catalysts are evaluated in sulfuric acid solution containing 1 M formic acid using linear sweeping voltammetry and chronoamperometry. The results show that Pd₅Ru₁/C displays the best electrocatalytic performance among all catalysts for formic acid electrooxidation.