Self-organized ZnAl2O4 nanostructures grown on -sapphire

Self-organized ZnAl₂O₄ nanostructures with the appearance (in SEM) of high aspect ratio horizontal nanowires are grown on uncatalysed c-sapphire by vapour phase transport. The nanostructures grow as three equivalent crystallographic variants on c-sapphire. Raman and cathodoluminescence spectroscopy confirm that the nanostructures are not ZnO and TEM shows that they are the cubic spinel, zinc aluminate, ZnAl₂O₄, formed by the reaction of Zn and O with the sapphire substrate.     

Paper-substrate room-temperature phosphorescence of phenothiazine derivatives enhanced by thallium(I) nitrate and surface-active agents

The effects of anionic, non-ionic, and cationic surfactants and thallium(I) nitrate on the paper-substrate room-temperature phosphorescence (RTP) of eleven phenothiazine derivatives are described. Enhancement factors within the range 1.5–10 are observed after addition of sodium dodecylsulfate, dodecyltrimethylammonium chloride and thallium(I) nitrate. The influence of surfactant on phosphor characteristics as well as effects of moisture are discussed. Limits of detection were in the range 0.2–2 ng. Results are also reported for p-aminobenzoic acid, carbazole and o-terphenyl.     

Reductive activation of nitrate reductases

Protein film voltammetry of Paracoccus pantotrophus respiratory nitrate reductase (NarGH) and Synechococcus elongatus assimilatory nitrate reductase (NarB) shows that reductive activation of these enzymes may be required before steady state catalysis is observed. For NarGH complementary spectroscopic studies suggest a structural context for the activation. Catalytic protein film voltammetry at a range of temperatures has allowed quantitation of the activation energies for nitrate reduction. For NarGH with an operating potential of ca. 0.05 V the activation energy of ca. 35 kJ mol-1 is over twice that measured for NarB whose operating potential is ca. -0.35 V.     

Elucidation of the initial step of oligonucleotide fragmentation in matrix-assisted laser desorption/ionization using modified nucleic acids

To probe the mechanism of gas-phase oligonucleotide ion fragmentation, modified oligonucleotides were studied using matrix-assisted laser desorption/ionization. The oligonucleotides were of the form 5'-TTTTXTTTTT, where X was a modified nucleotide. Modifications included substitution of hydroxy, methoxy, amino, and allyl groups at the 2'-position of the deoxyribose. The modified ribose contained adenine, guanine, cytosine, or uracil bases. For comparison, we studied oligomers where X was an unmodified adenosine, guanosine, cytidine, thymidine, or uridine deoxyribonucleotide. We found a very strong dependence of the matrix-to-analyte ratio on fragmentation for these oligomers. Analysis of these modifications suggests that the initial fragmentation step in MALDI-MS involves a two-step (E1) elimination of the base.     

An experimentally validated rod model for soft continuum robots

Soft robots are bio-inspired, highly deformable robots with the ability to interact with workpieces in a manner that complements their hard robot counterparts. To develop practical applications and reproducible designs of soft robots, new models are necessary to describe their kinematics and dynamics. In the present work, we describe experimental and numerical investigations of a popular pneumatically-actuated soft continuum arm. These works enable us to derive constitutive relations and develop a rod model for large deformations of the arm that faithfully describes its bending behavior. We show how the resulting non-classical constitutive relation can be defined either through experiments or through quasi-static finite element simulations. With the help of this relation, the resulting rod model can be used to study the dynamics of the soft robot arm in a fast and tractable manner. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of pharmaceuticals on thermoreversible gelation of PEO-PPO-PEO copolymers

Pluronic F127, a triblock copolymer of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), has generated considerable interest as a drug delivery vehicle due to its ability to gel at physiological temperatures. This work examines the gelation behavior of Pluronic F127 in the presence of a series of hydrophobic pharmaceuticals, to determine whether there is any correlation between gelation and physicochemical parameters of drug solutes. The study includes the local anesthetics dibucaine, lidocaine, and tetracaine; the pharmaceutical additives methyl paraben, ethyl paraben, and propyl paraben; the anti-cancer agents paclitaxel and baccatin III; and the anti-inflammatory agent sulindac. The results indicate that the presence of local anesthetics and pharmaceutical additives allows F127 solutions to form gels at lower copolymer concentrations; local anesthetics and pharmaceutical additives also shift gelation down to a lower gelation temperature. This behavior is strongly dependent on drug solubility; poorly soluble drugs (paclitaxel, baccatin III, sulindac) do not change the lower gelation temperature or minimum F127 concentration for gelation. An equation relating the decrease in gelation temperature to drug solubility is presented, and the equation fits the data well. The results have significant positive implications on the toxicity and economic issues related to use of Pluronic F127 in drug delivery.     

Enhancing the intensities of lysine-terminated tryptic peptide ions in matrix-assisted laser desorption/ionization mass spectrometry

Tryptic digests of three proteins are reacted with O-methylisourea in order to convert lysine residues to homoarginines. The resulting homoarginine-terminated peptides exhibit more intense MALDI mass spectral peaks than their lysine-terminated predecessors. This simple chemical reaction should therefore facilitate protein sequencing and mass mapping.     

Comparison of the precision of estimation of copolymerization reactivity ratios by current methods

Six recently proposed methods for analyzing copolymerization composition data have been compared to a nonlinear least-squares analysis to ascertain the precision of the six methods in determining reactivity ratios. Data used were simulated for five hypothetical monomer pairs with three different types of experiment design and contained error structures similar to those observed experimentally. The results of the comparisons suggest that retrospective analyses of existing copolymerization data should only be done with a nonlinear least-squares analysis. For new data, the design of experiments is of great importance, and when done properly allows the use of some of the linear least-squares methods of analysis.