Shape-Selective Electroless Plating within Expanding Template Pores: Etching-Assisted Deposition of Spiky Nickel Nanotube Networks.

Nano-objects are favored structures for applications such as catalysis and sensing. Although they already provide a large surface-to-volume ratio, this ratio can be further increased by shape-selective plating of the nanostructure surfaces. This process combines the conformity of autocatalytic deposition with the defined nucleation and growth characteristics of colloidal nanoparticle syntheses. However, many aspects of such reactions are still not fully understood. In this study, we investigate in detail the growth of spiky nickel nanotubes in polycarbonate template membranes. One distinctive feature of our synthesis is the simultaneous growth of nanospikes on both the inside and outside of nanotubes while the tubes are still embedded in the polymer. This is achieved by combining the plating process with locally enhanced in situ etching of the poylmer template, for which we propose a theory. Electron microscopy investigations reveal twinning defects as the driving force for the growth of crystalline nanospikes. Deposit crystallinity is ensured by the reducing agent hydrazine. Iminodiacetic acid is not only used as a complexing agent during synthesis but apparently also acts as a capping agent and limits random nucleation on the spike facets. Finally, we apply our synthesis to templates with interconnected pores to obtain free-standing spiky nickel nanotube networks, demonstrating its ability to homogeneously coat substrates with extended inner surfaces and to operate in nanoscale confinement.

Template-Free Electroless Plating of Gold Nanowires: Direct Surface Functionalization with Shape-Selective Nanostructures for Electrochemical Applications.

Metal nanowires (NWs) represent a prominent nanomaterial class, the interest in which is fueled by their tunable properties as well as their excellent performance in, for example, sensing, catalysis, and plasmonics. Synthetic approaches to obtain metal NWs mostly produce colloids or rely on templates. Integrating such nanowires into devices necessitates additional fabrication steps, such as template removal, nanostructure purification, or attachment. Here, we describe the development of a facile electroless plating protocol for the direct deposition of gold nanowire films, requiring neither templates nor complex instrumentation. The method is general, producing three-dimensional nanowire structures on substrates of varying shape and composition, with different seed types. The aqueous plating bath is prepared by ligand exchange and partial reduction of tetrachloroauric acid in the presence of 4-dimethylaminopyridine and formaldehyde. Gold deposition proceeds by nucleation of new grains on existing nanostructure tips and thus selectively produces curvy, polycrystalline nanowires of high aspect ratio. The nanofabrication potential of this method is demonstrated by producing a sensor electrode, whose performance is comparable to that of known nanostructures and discussed in terms of the catalyst architecture. Due to its flexibility and simplicity, shape-selective electroless plating is a promising new tool for functionalizing surfaces with anisotropic metal nanostructures.

Free-Standing Networks of Core-Shell Metal and Metal Oxide Nanotubes for Glucose Sensing.

Nanotube assemblies represent an emerging class of advanced functional materials, whose utility is however hampered by intricate production processes. In this work, three classes of nanotube networks (monometallic, bimetallic, and metal oxide) are synthesized solely using facile redox reactions and commercially available ion track membranes. First, the disordered pores of an ion track membrane are widened by chemical etching, resulting in the formation of a strongly interconnected pore network. Replicating this template structure with electroless copper plating yields a monolithic film composed of crossing metal nanotubes. We show that the parent material can be easily transformed into bimetallic or oxidic derivatives by applying a second electroless plating or thermal oxidation step. These treatments retain the monolithic network structure but result in the formation of core-shell nanotubes of altered composition (thermal oxidation: Cu2O-CuO; electroless nickel coating: Cu-Ni). The obtained nanomaterials are applied in the enzyme-free electrochemical detection of glucose, showing very high sensitivities between 2.27 and 2.83 A M-1 cm-2. Depending on the material composition, varying reactivities were observed: While copper oxidation reduces the response to glucose, it is increased in the case of nickel modification, albeit at the cost of decreased selectivity. The performance of the materials is explained by the network architecture, which combines the advantages of one-dimensional nano-objects (continuous conduction pathways, high surface area) with those of a self-supporting, open-porous superstructure (binder-free catalyst layer, efficient diffusion). In summary, this novel synthetic approach provides a fast, scalable, and flexible route toward free-standing nanotube arrays of high compositional complexity.

Evaluation of insulin-like growth factor-1, total thyroxine, feline pancreas-specific lipase and urinary corticoid-to-creatinine ratio in cats with diabetes mellitus in Switzerland and the Netherlands.

Objectives The aim of the study was to evaluate circulating insulin-like growth factor-1 (IGF-1), feline pancreas-specific lipase (fPLI) and total thyroxine (TT4) concentrations and urinary corticoid-to-creatinine ratio (UCCR) as indicators for the prevalence of acromegaly, pancreatitis, hyperthyroidism and hypercortisolism in cats with diabetes mellitus. Methods Blood and urine samples were collected from diabetic cats treated in primary care clinics in Switzerland and the Netherlands. Standardised questionnaires and physical examination forms provided clinical information from owners and veterinarians. Laboratory testing included serum biochemistry profile analysis and measurement of circulating fructosamine, IGF-1, fPLI, and TT4 concentrations and UCCR. CT of the pituitary gland was performed using a multidetector computed tomography scanner. Results Blood samples were available from 215 cats and urine samples were collected at home from 117 cats. Age ranged from 2-18 years (median 12 years) and body weight from 2.7-12.3 kg (median 5.5 kg). Sixty-five percent of the cats were castrated male and 35% were female (33% spayed); 82% were domestic shorthair cats. Eighty percent of cats received a porcine insulin zinc suspension, 19.5% insulin glargine and 0.5% a human neutral protamine hagedorn insulin. Thirty-six of 202 (17.8%) cats had IGF-1 concentrations >1000 ng/ml. Serum fPLI, and TT4 concentrations and UCCR were increased in 86/196 (43.9%), 9/201 (4.5%) and 18/117 cats (15.3%), respectively. Prevalence did not differ between countries. Conclusions Hyperthyroidism is rare, whereas increased fPLI concentration, possibly reflecting pancreatitis, is common in diabetic cats. The high UCCR may reflect activation of the hypothalamus-pituitary-adrenal axis, which also occurs in diabetic humans. The percentage of cats with increased IGF-1 was high but lower than reported in recent studies.

Characterization of recombinant human and bovine thyroid-stimulating hormone preparations by mass spectrometry and determination of their endotoxin content.

BACKGROUND: The TSH stimulation test to confirm canine hypothyroidism is commonly performed using a recombinant human TSH (rhTSH), as up to date, canine TSH is not yet commercially available. Limiting factors for the use of rhTSH are its high costs and occasional difficulties in product availability. Less expensive bovine TSH preparations (bTSH) purified from bovine pituitary glands are readily commercially available. The aim of this study was to evaluate two different bTSH products as alternative to rhTSH using mass spectrometry. RESULTS: More than 50 proteins, including other pituitary hormones, bovine albumin, hemoglobin, and tissue proteins were identified in the bTSH preparations. In contrast, rhTSH proved to be a highly pure product. Significantly higher endotoxin levels could be detected in all bTSH products compared to the rhTSH. CONCLUSIONS: Both bTSH products are crude mixtures and therefore not an acceptable alternative to rhTSH. Their use should be discouraged to prevent unintended side effects.

Modulation of oxidative cell damage by reconstituted mixtures of phenolic apple juice extracts in human colon cell lines.

Diets rich in fruits and vegetables are associated with a lower risk of tumour induction in the intestine and other sites. Apple juice with high amounts of antioxidative phenolics might protect the intestine against reactive oxygen species-mediated cell damage. We investigated to which extent the preventive effectiveness of polyphenolic juice extracts is governed by the amounts of five major constituents (rutin, phloridzin, chlorogenic acid, caffeic acid and epicatechin). In human colon cell lines (Caco-2, HT29), reconstituted mixtures of these phenolics were investigated in comparison to the original juice extracts, originating from cider and table apples. Parameters studied were (oxidative) DNA damage (Comet assay), cellular redox status (dichlorofluorescein assay) and Trolox equivalent antioxidant capacity (TEAC). The TEAC of the reconstituted mixtures was higher compared to the respective original extracts (4.7-7.3 mM vs. 3.6-4.2 mM Trolox). After 24 h cell incubation, menadione-induced (oxidative) DNA damage was more effectively reduced by the reconstituted mixtures (1-100 microg/mL, 24 h), as compared to the original extracts. In contrast, the cellular ROS level was reduced to a rather similar extent by original extracts and reconstituted mixtures. The results lead to the conclusion that the selected constituents in their authentic proportions substantially account for the antioxidative effectiveness of phenolic apple juice extracts.

Polyphenolic apple juice extracts and their major constituents reduce oxidative damage in human colon cell lines.

Apple juice containing high amounts of antioxidative polyphenols might protect the intestine against oxidative cell damage. We investigated the preventive effectiveness of polyphenolic juice extracts of different origins (cider and table apples) in comparison to their major constituents in human colon cell lines (Caco-2, HT29). Parameters studied were (oxidative) DNA damage (Comet assay), glutathione level (photometric kinetic assay), cellular redox status (dichlorofluorescein assay) and antioxidant capacity. The extracts (50-250 microg/mL) modulated DNA damage and redox status in a concentration-dependent manner at 24-h incubation. The pomace extraction technology, applied for juice preparation, and the preferential selection of cider apple varieties influenced the polyphenolic pattern and increased the biological effectiveness of the extracts. The preventive potential of major juice constituents (1-100 microM, 24 h) strongly differed: rutin, epicatechin and caffeic acid clearly reduced (oxidative) DNA damage (Caco-2), chlorogenic acid efficiently decreased cellular reactive oxygen species level (HT29, Caco-2). The aglyca quercetin and phloretin exhibited the highest preventive/antioxidant capacity in all assays. The stability of the compounds inversely correlated with their preventive effectiveness and might contribute to the observed cell specific sensitivities. In conclusion, apple juice extracts distinctly reduce oxidative cell damage in human colon cell lines, an effect, which in part can be accounted for by their major constituents.