Dihydroazulene Photoswitch Operating in Sequential Tunneling Regime: Synthesis and Single‐Molecule Junction Studies

Molecular switches play a central role for the development of molecular electronics. In this work it is demonstrated that the reproducibility and robustness of a single‐molecule dihydroazulene (DHA)/vinylheptafulvene (VHF) switch can be remarkably enhanced if the switching kernel is weakly coupled to electrodes so that the electron transport goes by sequential tunneling. To assure weak coupling, the DHA switching kernel is modified by incorporating p‐MeSC₆H₄ end‐groups. Molecules are prepared by Suzuki cross‐couplings on suitable halogenated derivatives of DHA. The synthesis presents an expansion of our previously reported bromination–elimination–cross‐coupling protocol for functionalization of the DHA core. For all new derivatives the kinetics of DHA/VHF transition has been thoroughly studied in solution. The kinetics reveals the effect of sulfur end‐groups on the thermal ring‐closure of VHF. One derivative, incorporating a p‐MeSC₆H₄ anchoring group in one end, has been placed in a silver nanogap. Conductance measurements justify that transport through both DHA (high resistivity) and VHF (low resistivity) forms goes by sequential tunneling. The switching is fairly reversible and reenterable; after more than 20 “ON‐OFF” switchings, both DHA and VHF forms are still recognizable, albeit noticeably different from the original states.     

Nitrous oxide emissions from two sites in Southern England during winter 1981/1982

Nitrous oxide fluxes from soil surfaces were measured during winter 1981/82 on two fallow sites, a loamy sand and a clay loam, that had been watered to field capacity and fertilised at the rate of 200 kg N ha^?1 on the 5 October 1981. Highest fluxes were obtained in the sampling period immediately after fertiliser application. They were in the range 3.5–20 g N₂O? N ha^?1 day^?1 on the loamy sand, and declined rapidly from a peak of almost 165 g N₂O? N ha^?1 day^?1 on the day following fertiliser application on the clay loam. The temperature during this period was in the range 6.5 to 14°C. As soil temperature declined during the sampling periods in December (?2 to 3°C) and February (4.5 to 6.5°C) and nitrate was leached in the subsoil, N₂O evolution became very low (<1 g N₂O? N ha^?1 day^?1). Rainfall over the whole sampling period from early October to mid-February was 282 mm. On both sites there was a very high degree of variability within the sites at any sampling time.     

Glycosidic linkages of legume,grass and cereal straw cell walls before and after extensive degradation by rumen microorganisms

The technique of methylation analysis for the location of glycosidic linkages in cell wall polysaccharides was applied directly (after dry milling in liquid nitrogen) to whole wheat and barley straws, cell wall preparations from early- and late-cut perennial ryegrass and white clover, and their extensively degraded residues recovered from the rumen. The addition of an internal standard, methyl-β-D-allo-pyranose, to milled samples enabled the recovery of partially-methylated sugars to be quantified, and the recovery of parent sugars from methylated material to be compared with values obtained by direct estimation of monosaccharides by the alditol acetate method. Recovery of sugars from methylated samples was generally higher than that predicted by the alditol acetate method, particularly from digested residues. All four samples of Gramineae showed similar proportions of glycosidic linkages in which (1 →4)-linked xylose and glucose units accounted for more than 80% of total identified partially-methylated sugars. The proportions of glycosidic linkages found in digested residues of straws were essentially the same as those found in the parent material. In residues of the more digestible ryegrass there was a two- to three-fold increase in (1→4)-linked xylose units without branch points at the O-2/O-3 positions, the proportions of these branch points being substantially reduced. A corresponding reduction in the proportion of (1→2)-, (1→3)-and terminally-linked arabinose units was also found. The proportion of both (1→4)- and (1→3)-linked glucose units were also reduced in digested residues. These changes were greater in the early-cut than in the late-cut sample. White clover differed from the Gramineae in a number of respects. Galactose units predominantly in the form of (1→4)-, (1→6)- and terminally-linked units, were the major non-cellulosic sugars present. The proportion of all forms of galactose was reduced in digested residues, but (1→6)-linked units appeared more resistant to degradation than (1→4)-linked units. Like ryegrass, the proportion of xylose units increased in digested residues from clover, while the proportion of glucose decreased. The proportion of (1→4)-linked mannose units, initially present at levels ten times as great as in the Gramineae, was also substantially reduced.     

Automated design of robust discriminant analysis classifier for foot pressure lesions using kinematic data

In the recent years, the use of motion tracking systems for acquisition of functional biomechanical gait data, has received increasing interest due to the richness and accuracy of the measured kinematic information. However, costs frequently restrict the number of subjects employed, and this makes the dimensionality of the collected data far higher than the available samples. This paper applies discriminant analysis algorithms to the classification of patients with different types of foot lesions, in order to establish an association between foot motion and lesion formation. With primary attention to small sample size situations, we compare different types of Bayesian classifiers and evaluate their performance with various dimensionality reduction techniques for feature extraction, as well as search methods for selection of raw kinematic variables. Finally, we propose a novel integrated method which fine-tunes the classifier parameters and selects the most relevant kinematic variables simultaneously. Performance comparisons are using robust resampling techniques such as Bootstrap 632+ and k-fold cross-validation. Results from experimentations with lesion subjects suffering from pathological plantar hyperkeratosis, show that the proposed method can lead to approximately 96% correct classification rates with less than 10% of the original features.     

Yield Strengths of Biaxially Textured Metallic Substrates (Ni and its Alloys) Determined Using a Simplified Test Method

A simple testing method is used to compare the yield strengths (YS) of biaxially textured metallic substrates (Ni and its alloys) presently under development for YBa₂Cu₃O_7−x coated conductors. This method is based on a retired ASTM D3379 tensile test standard method that was originally recommended for single filament materials. Several common textured substrates, such as Ni, Ni-3at.%W, and Ni-5at.%W, procured from different manufacturers, were tested using this method, and the data were compared with the values reported in the literature. A new alloy substrate (constantan (Cu55-Ni44-Mn1wt.%)) that is biaxially textured in-house was also tested using this method, and the YS data were compared with those of other substrates. For the substrates used in this study, the data obtained using this method indicated that Ni substrates have YS of ∼52 MPa, Ni-3at.%W substrates have YS of ∼106 MPa, Ni-5at.%W substrates have YS 163 MPa, and Cu55-Ni44-Mn1 wt.% substrates have YS of 74 MPa.     

Treatment of milk by gamma irradiation—effect of anoxia on lipid peroxidation and the survival of Pseudomonas aeruginosa

One of the causes of organoleptic changes in milk, lipid peroxidation, has been monitored by a sensitive assay newly applied to foodstuffs. It has been shown that even at medium radiation doses (up to 3600 Gy) negligible lipid peroxidation takes place, providing the milk is thoroughly gassed with nitrogen. Using a test spoilage microorganism, Pseudomonas aeruginosa (Schroeter), it was shown that the D₁₀ was 35 Gy in air and 105 Gy under anaerobic conditions. Dose/survival curves indicate that 5 decades of killing needed 200 Gy in air and 600 Gy under nitrogen. However, even after receiving a dose of 1600 Gy, both aerobically and anaerobically treated milk failed the methylene blue test at 21 days post-irradiation. The data indicate that, although the deleterious lipid peroxidation effects of irradiation can be minimised by the removal of air, this in turn results in a degree of protection being afforded to the bacteria, and that doses in excess of 1600 Gy are needed to effectively sterilise milk.     

Polydopamine Encapsulation of Fluorescent Nanodiamonds for Biomedical Applications

Fluorescent nanodiamonds (FNDs) are promising bioimaging probes compared with other fluorescent nanomaterials such as quantum dots, dye‐doped nanoparticles, and metallic nanoclusters, due to their remarkable optical properties and excellent biocompatibility. Nevertheless, they are prone to aggregation in physiological salt solutions, and modifying their surface to conjugate biologically active agents remains challenging. Here, inspired by the adhesive protein of marine mussels, encapsulation of FNDs within a polydopamine (PDA) shell is demonstrated. These PDA surfaces are readily modified via Michael addition or Schiff base reactions with molecules presenting thiol or nitrogen derivatives. Modification of PDA shells by thiol terminated poly(ethylene glycol) (PEG‐SH) molecules to enhance colloidal stability and biocompatibility of FNDs is described. Their use as fluorescent probes for cell imaging is demonstrated; it is found that PEGylated FNDs are taken up by HeLa cells and mouse bone marrow‐derived dendritic cells and exhibit reduced nonspecific membrane adhesion. Furthermore, functionalization with biotin‐PEG‐SH is demonstrated and long‐term high‐resolution single‐molecule fluorescence based tracking measurements of FNDs tethered via streptavidin to individual biotinylated DNA molecules are performed. This robust polydopamine encapsulation and functionalization strategy presents a facile route to develop FNDs as multifunctional labels, drug delivery vehicles, and targeting agents for biomedical applications.     

A Modular Vaccine Platform Combining Self‐Assembled Peptide Cages and Immunogenic Peptides

Subunit vaccines use delivery platforms to present minimal antigenic components for immunization. The benefits of such systems include multivalency, self‐adjuvanting properties, and more specific immune responses. Previously, the design, synthesis, and characterization of self‐assembling peptide cages (SAGEs) have been reported. In these, de novo peptides are combined to make hubs that assemble into nanoparticles when mixed in aqueous solution. Here it is shown that SAGEs are nontoxic particles with potential as accessible synthetic peptide scaffolds for the delivery of immunogenic components. To this end, SAGEs functionalized with the model antigenic peptides tetanus toxoid_632‐651 and ovalbumin_323‐339 drive antigen‐specific responses both in vitro and in vivo, eliciting both CD4⁺ T cell and B cell responses. Additionally, SAGEs functionalized with the antigenic peptide hemagglutinin_518‐526 from the influenza virus are also able to drive a CD8⁺ T cell response in vivo. This work demonstrates the potential of SAGEs to act as a modular scaffold for antigen delivery, capable of inducing and boosting specific and tailored immune responses.     

Extracellular recordings from patterned neuronal networks using planar microelectrode arrays

Neuronal cell networks have been reconstructed on planar microelectrode arrays (MEAs) from dissociated hippocampal pyramidal neurons. Microcontact printing (microCP) and a photoresist-liftoff method were used to selectively localize poly-L-lysine (PLL) on the surface of MEAs. Haptotaxis led to the organization of the neurons into networks localized adjacent to microelectrodes. Various grids of PLL with 2-25-microm-wide lines spaced by 50-200 microm with 15-25-microm nodes at intersection points were used to guide cell body attachment and neurite outgrowth. Bursting activity with spike amplitude attenuation was observed, and multichannel recordings detected instances of coincident firing activity. Finally, we present here an extracellular recording from a approximately 2 microm bundle of guided neurites.