3Y‐TZP In‐Depth Phase Transformation by Raman Spectroscopy: A Comparison of Three Methods

Zirconia phase transformation is usually studied on surface. For in‐depth study, three methods were proposed using Raman microspectroscopy quantitative evaluation: direct measurement on sample cross section, confocal Raman spectroscopy (CRS), and progressive pinhole aperture enlargement (PPAE). The aim of this study was to compare transformation profiles obtained with these three methods on the same sample. Three 3Y‐TZP samples were aged, respectively, for 25, 72, and 90 h in artificial saliva. Transformation profiles were determined with cross‐sectional measurement, CRS and PPAE. A transformation profile simulation model based on PPAE measurements is proposed, using the convolution of the excitation intensity profile and the Beer–Lambert law (optical properties of zirconia). The simulation model was validated with the determination of 3Y‐TZP transformation factor, T = 1.15 μm^?1, identical for the three aging durations. Both cross section and PPAE measured similar in‐depth transformation decrease, but with a 10 μm‐shift: transformed zirconia layer is more important in cross‐sectional protocol (36 μm with PPAE and 46 μm with cross‐sectional after 90 h aging). Complementary measurements on a 10 h aged sample, where transformation is initiated by Low‐Temperature Degradation, showed that sample preparation and polishing, necessary in the cross‐sectional method, were responsible for the higher transformation. PPAE method enables noninvasive in‐depth measurements with limited optical and mechanical biases.     

Taming the Reactivity of Monoterpene Synthases To Guide Regioselective Product Hydroxylation

Monoterpenoids are industrially important natural products with applications in the flavours, fragrances, fuels and pharmaceutical industries. Most monoterpenoids are produced by plants, but recently two bacterial monoterpene synthases have been identified, including a cineole synthase (bCinS). Unlike plant cineole synthases, bCinS is capable of producing nearly pure cineole from geranyl diphosphate in a complex cyclisation cascade that is tightly controlled. Here we have used a multidisciplinary approach to show that Asn305 controls water attack on the α-terpinyl cation and subsequent cyclisation and deprotonation of the α-terpineol intermediate, key steps in the cyclisation cascade which direct product formation towards cineole. Mutation of Asn305 results in variants that no longer produce α-terpineol or cineole. Molecular dynamics simulations revealed that water coordination is disrupted in all variants tested. Quantum mechanics calculations indicate that Asn305 is most likely a (transient) proton acceptor for the final deprotonation step. Our synergistic approach gives unique insight into how a single residue, Asn305, tames the promiscuous chemistry of monoterpene synthase cyclisation cascades. It does this by tightly controlling the final steps in cineole formation catalysed by bCinS to form a single hydroxylated monoterpene product.     

Porphyrins as Colorimetric and Photometric Biosensors in Modern Bioanalytical Systems

Advances in porphyrin chemistry have provided novel materials and exciting technologies for bioanalysis such as colorimetric sensor array (CSA), photo-electrochemical (PEC) biosensing, and nanocomposites as peroxidase mimetics for glucose detection. This review highlights selected recent advances in the construction of supramolecular assemblies based on the porphyrin macrocycle that provide recognition of various biologically important entities through the unique porphyrin properties associated with colorimetry, spectrophotometry, and photo-electrochemistry.     

Two-Step Autohydrolysis Pretreatment: Towards High Selective Full Fractionation of Wheat Straw

Pretreatment is necessary to increase the enzymatic digestibility of lignocellulosic biomass. Here, degradation reactions of solubilized pentoses to furfural and others are undesired regarding the reduced product yield and increasing downstream processing efforts. In this work, the use of the unit operation configuration was successfully shown to reduce degradation reactions. In the used two-step autohydrolysis pretreatment, the reaction is stopped before degradation takes place. The pentoses are removed by water leaching to make them unavailable for degradation in a second autohydrolysis treatment. The overall sugars yield is increased, and the furfural formation is decreasing while maintaining the high lignin purity using the two-step autohydrolysis pretreatment.     

Tuning G-Quadruplex Nanostructures with Lipids. Towards Designing Hybrid Scaffolds for Oligonucleotide Delivery

Two G-quadruplex forming oligonucleotides [d(TG₄T)₄ and d(TG₆T)₄] were selected as two tetramolecular quadruplex nanostructures because of their demonstrated ability to be modified with hydrophobic molecules. This allowed us to synthesize two series of G-quadruplex conjugates that differed in the number of G-tetrads, as well as in the terminal position of the lipid modification. Both solution and solid-phase syntheses were carried out to yield the corresponding lipid oligonucleotide conjugates modified at their 3′- and 5′-termini, respectively. Biophysical studies confirmed that the presence of saturated alkyl chains with different lengths did not affect the G-quadruplex integrity, but increased the stability. Next, the G-quadruplex domain was added to an 18-mer antisense oligonucleotide. Gene silencing studies confirmed the ability of such G-rich oligonucleotides to facilitate the inhibition of target Renilla luciferase without showing signs of toxicity in tumor cell lines.     

Limits of High Recovery Inland Desalination: Closed-Circuit Reverse Osmosis – a Viable Option?

Cost-efficient operation of inland brackish water reverse osmosis (BWRO) demands a high recovery. As recovery of BWRO is often limited to scaling, antiscalants (AS) are applied, whose environmental impact is disputed. In this paper, different systems (conventional single- and two-stage plug flow RO (PFRO) and closed-circuit RO (CCRO)) were simulated in various configurations (AS dosing, ion exchange (IEX) pretreatment, elements per vessel) to determine the recovery limiting factor for a hard feed. The novel proposed IEX-CCRO reached the highest recovery without AS dosing. PFRO configurations had lower recoveries, mainly due to hydraulic limitations. Utilizing RO brine reduced both the water demand and salts necessary for IEX regeneration.     

Electrical Actuation of Coated and Composite Fibers Based on Poly[ethylene-co-(vinyl acetate)]

Robots are typically controlled by electrical signals. Resistive heating is an option to electrically trigger actuation in thermosensitive polymer systems. In this study electrically triggerable poly[ethylene-co-(vinyl acetate)] (PEVA)-based fiber actuators are realized as composite fibers as well as polymer fibers with conductive coatings. In the coated fibers, the core consists of crosslinked PEVA (cPEVA), while the conductive coating shell is achieved via a dip coating procedure with a coating thickness between 10 and 140 µm. The conductivity of coated fibers σ = 300–550 S m⁻¹ is much higher than that of the composite fibers σ = 5.5 S m⁻¹. A voltage (U) of 110 V is required to heat 30 cm of coated fiber to a targeted temperature of ≈ 65 °C for switching in less than a minute. Cyclic electrical actuation investigations reveal ε′_rev = 5 ± 1% reversible change in length for coated fibers. The fabrication of such electro-conductive polymeric actuators is suitable for upscaling so that their application potential as artificial muscles can be explored in future studies.     

Safer energetic materials by a nanotechnological approach

Energetic materials - explosives, thermites, populsive powders - are used in a variety of military and civilian applications. Their mechanical and electrostatic sensitivity is high in many cases, which can lead to accidents during handling and transport. These considerations limit the practical use of some energetic materials despite their good performance. For industrial applications, safety is one of the main criteria for selecting energetic materials. The sensitivity has been regarded as an intrinsic property of a substance for a long time. However, in recent years, several approaches to lower the sensitivity of a given substance, using nanotechnology and materials engineering, have been described. This feature article gives an overview over ways to prepare energetic (nano-)materials with a lower sensitivity.     

Detection of low levels of long‐chain branching in polydisperse polyethylene materials

Creep experiments have been applied to probe the zero‐shear viscosity, η₀, of polyethylene chains directly and precisely in a constant‐stress rheometer at 190°C. Such experiments, when combined with precise measurements of the weight‐average molecular weight, M_w, calibrated relative to linear chains of high‐density polyethylene, are shown to provide a very sensitive approach to detect low levels (0.005 branches per 1000 carbons) of long‐chain branching (LCB). This detection limit is shown to be insensitive to whether the molecular weight distribution (MWD) breadth, M_w/M_n, rises from about two to ten. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Spinal Cord T-Cell Infiltration in the Rat Spared Nerve Injury Model: A Time Course Study

The immune system is involved in the development of neuropathic pain. In particular, the infiltration of T-lymphocytes into the spinal cord following peripheral nerve injury has been described as a contributor to sensory hypersensitivity. We used the spared nerve injury (SNI) model of neuropathic pain in Sprague Dawley adult male rats to assess proliferation, and/or protein/gene expression levels for microglia (Iba1), T-lymphocytes (CD2) and cytotoxic T-lymphocytes (CD8). In the dorsal horn ipsilateral to SNI, Iba1 and BrdU stainings revealed microglial reactivity and proliferation, respectively, with different durations. Iba1 expression peaked at D4 and D7 at the mRNA and protein level, respectively, and was long-lasting. Proliferation occurred almost exclusively in Iba1 positive cells and peaked at D2. Gene expression observation by RT-qPCR array suggested that T-lymphocytes attracting chemokines were upregulated after SNI in rat spinal cord but only a few CD2/CD8 positive cells were found. A pronounced infiltration of CD2/CD8 positive T-cells was seen in the spinal cord injury (SCI) model used as a positive control for lymphocyte infiltration. Under these experimental conditions, we show early and long-lasting microglia reactivity in the spinal cord after SNI, but no lymphocyte infiltration was found.