Influence of Gold Nanoparticle Film Porosity on the Chemiresistive Sensing Performance

The porosity of 1‐hexanethiol‐functionalised gold nanoparticle films was assessed and utilised as chemiresistor sensors. Electrochemical capacitance measurements showed that the accessibility of electrolytes of different ionic strengths into the pores depended on the thickness of the electric double layer formed. A large variation in capacitance was measured in 0.01–1000 mM NaClO₄, implying a wide pore size distribution. The change in morphology of the nanoparticle films upon storage in air, water and ethanol for two weeks was investigated. There was a significant decrease in the electrochemical capacitance at high electrolyte concentrations for the ethanol‐stored films compared to the freshly‐prepared films suggesting a decrease in the number of small pores of radii in the range of 0.3–3 nm. This was further supported by optical topographical measurements where a decrease in the thickness of ethanol‐stored films was observed relative to the freshly‐prepared films. The porous nature of the nanoparticle films was found to have an effect on the chemical sensing behaviour. When used as chemiresistor sensors, for the detection of heptane in water, the ethanol‐stored films provided larger resistance changes and longer response times. This suggests that the more densely packed ethanol‐stored films provided more sites that enabled film swelling, and that diffusion of the analyte occurred through the narrower water‐filled pores. This demonstrates the effect of different storage conditions on film morphology and subsequently sensor response.     

Bioluminescence in Dinoflagellates: Evidence that the Adaptive Value of Bioluminescence in Dinoflagellates is Concentration Dependent

Three major hypotheses have been proposed to explain why dinoflagellate bioluminescence deters copepod grazing: startle response, aposematic warning, and burglar alarm. These hypotheses propose dinoflagellate bioluminescence (A) startles predatory copepods, (B) warns potential predators of toxicity, and (C) draws the attention of higher order visual predators to the copepod's location. While the burglar alarm is the most commonly accepted hypothesis, it requires a high concentration of bioluminescent dinoflagellates to be effective, meaning the bioluminescence selective advantage at lower, more commonly observed, dinoflagellate concentrations may result from another function (e.g. startle response or aposematic warning). Therefore, a series of experiments was conducted to evaluate copepod grazing (Acartia tonsa) on bioluminescent dinoflagellates (during bioluminescent and nonbioluminescent phases, corresponding to night and day, respectively) at different concentrations (10, 1000, and 3000 cells mL^?1), on toxic (Pyrodinium bahamense var. bahamense) and nontoxic (Lingulodinium polyedrum) bioluminescent dinoflagellates, and in the presence of nonluminescent diatoms (Thalassiosira eccentrica). Changes in copepod ingestion rates, clearance rates, and feeding preferences as a result of these experimental factors, particularly during the mixed trails with nonluminescent diatoms, indicate there is a concentration threshold at which the burglar alarm becomes effective and below which dinoflagellate bioluminescence functions as an aposematic warning.     

A New Photochemical Reaction of Sulfonic Acid Esters

Abstract

In 1968 Zen and coworkers reported that thep-tolylsulfonyl group could be removed from carbohydrate systems by photochemical reaction (eq 1).¹ Since then other investigators have used this deprotection process in carbohydrate synthesis.^2-10 Mechanistic studies^11-16 have shown that tosylate photolysis is promoted by compounds (e.g., triethylamine) that donate an electron to an excitedp-toluenesulfonate to generate a radical anion (1). This intermediate then fragments to form the anion of the deprotected sugar (Scheme 1). Since generating a radical anion is the central element in this photochemical process, structural changes that impact radical anion formation should influence the reaction. Replacing the p - tolylsulfonyl group with the pentafluorophenylsulfonyl group generates a more stable radical anion (2) because the electronegative fluorine atoms can help stabilize the negative charge. Since we have a continuing interest in the photochemistry of sulfonic acid esters, we synthesized the pentafluorobenzenesulfonates (pentaflates) 3-6 and studied their photochemistry under electron transfer conditions.     

Chemical Processes Involving 18-Crown-6-Ether in Activated Noncovalent Complexes with Protonated Peptides

These last decades, it has been widely assumed that 18-crown-6-ether (CE) plays a spectator role during the chemical processes occurring in isolated host-guest complexes between peptides or proteins and CE after activation in mass spectrometers. Our present experimental and theoretical results challenge this hypothesis by showing that CE can abstract a proton or a protonated molecule from protonated peptides after activation by collisions in argon or electron capture/transfer. Furthermore, thanks to comparison between experimental and calculated values of collision cross-sections, we demonstrate that CE can change binding site after electron transfer. We also propose detailed mechanisms for these processes.     

A result about a selection problem of Michael

It is shown that a continuum that is an space in the sense of Michael must be hereditarily decomposable. This improves known results, thereby providing more evidence that such continua must be dendrites.

     

All-Pairs Small-Stretch Paths

Let G = (V, E) be a weighted undirected graph. A path between u, v  V is said to be of stretch t if its length is at most t times the distance between u and v in the graph. We consider the problem of finding small-stretch paths between all pairs of vertices in the graph G.It is easy to see that finding paths of stretch less than 2 between all pairs of vertices in an undirected graph with n vertices is at least as hard as the Boolean multiplication of two n × n matrices. We describe three algorithms for finding small-stretch paths between all pairs of vertices in a weighted graph with n vertices and m edges. The first algorithm, STRETCH₂, runs in Õ(n^3/2m^1/2) time and finds stretch 2 paths. The second algorithm, STRETCH_7/3, runs in Õ(n^7/3) time and finds stretch 7/3 paths. Finally, the third algorithm, STRETCH₃, runs in Õ(n²) and finds stretch 3 paths.Our algorithms are simpler, more efficient and more accurate than the previously best algorithms for finding small-stretch paths. Unlike all previous algorithms, our algorithms are not based on the construction of sparse spanners or sparse neighborhood covers.     

Conjugacy classes and finite p-groups

Let G be a finite p-group, where p is a prime number, and a ∈ G. Denote by Cl(a) = {gag⁻¹| g ∈ G} the conjugacy class of a in G. Assume that |Cl(a)| = pⁿ. Then Cl(a) Cl(a⁻¹) = {xy | x ∈ Cl(a), y ∈ Cl(a⁻¹)} is the union of at least n(p − 1) + 1 distinct conjugacy classes of G. Received: 16 December 2004