Improving the sensitivity for DNA sensing based on double-anchored DNA modified gold nanoparticles

DNA modified nanoparticles (AuNPs) are an established and widely used type of nucleotide sensor. We sought to improve the design by applying short rigid DNA duplexes near the surface of the AuNPs forming a so called double-anchored AuNP sensor, and compared it with other conventional DNA modified AuNPs. The improved design exhibited higher assembly efficiency, and consequently increased its sensitivity to target DNA.     

Manganese-catalyzed epoxidations of alkenes in bicarbonate solutions

This paper describes a method, discovered and refined by parallel screening, for the epoxidation of alkenes. It uses hydrogen peroxide as the terminal oxidant, is promoted by catalytic amounts (1.0-0.1 mol %) of manganese(2+) salts, and must be performed using at least catalytic amounts of bicarbonate buffer. Peroxymonocarbonate, HCO(4)(-), forms in the reaction, but without manganese, minimal epoxidation activity is observed in the solvents used for this research, that is, DMF and (t)BuOH. More than 30 d-block and f-block transition metal salts were screened for epoxidation activity under similar conditions, but the best catalyst found was MnSO(4). EPR studies show that Mn(2+) is initially consumed in the catalytic reaction but is regenerated toward the end of the process when presumably the hydrogen peroxide is spent. A variety of aryl-substituted, cyclic, and trialkyl-substituted alkenes were epoxidized under these conditions using 10 equiv of hydrogen peroxide, but monoalkyl-alkenes were not. To improve the substrate scope, and to increase the efficiency of hydrogen peroxide consumption, 68 diverse compounds were screened to find additives that would enhance the rate of the epoxidation reaction relative to a competing disproportionation of hydrogen peroxide. Successful additives were 6 mol % sodium acetate in the (t)BuOH system and 4 mol % salicylic acid in the DMF system. These additives enhanced the rate of the desired epoxidation reaction by 2-3 times. Reactions performed in the presence of these additives require less hydrogen peroxide and shorter reaction times, and they enhance the yields obtained from less reactive alkene substrates. Possible mechanisms for the reaction are discussed.     

Solution- and solid-phase syntheses of substituted guanidinocarboxylic acids

A library of guanidine-based compounds was produced to mimic the lead compound 1, which is a substance known to have intensely sweet-taste characteristics. Libraries of guanidinocarboxylic acids were therefore prepared via two synthetic methods. The solid-phase method involving trapping of solution-phase carbodiimides by supported amines was used to produce N,N'-dialkyl derivatives (Scheme 1). The second solid-phase method, featuring supported carbodiimides and solution-phase amines (Scheme 2), was devised to prepare N,N'-disubstituted and N,N',N'-trisubstituted guanidinocarboxylic acids. A small collection of guanadinoacetic acid dimers and trimers was also prepared, but this time via a solution-phase coupling of carbodiimides to a polyamine linker.     

Solvation of transition metal complexes: thermochemical approaches

Conclusion and extensions We hope that this Review has made readers more aware of solvation of inorganic complexes, and of the importance of such knowledge in understanding their chemistryperhaps particularly their reactivity. The approach just set out for inorganic complexes should be of considerable value in the field or organometallic chemistry. In particular, informed use of solvation characteristics should help in optimising conditions for organometallic reactions and in homogeneous catalysis. Unfortunately, solvation data on reactants are too sparse (the subject index ofComprehensive Organometallic Chemistry contains justthree entries under solubility!) for serious examination of reactivity trends in terms of initial state and transition state contributions to be possible in almost all areas. Moreover, there are some fundamental problems over transfer parameters. Thus, a favourite electrochemical assumption is that the ferrocene/ferrocinium redox potential is independent of solvent. Yet, the dependence of rate constants on medium for outer-sphere electron transfer in the ferrocene/ferrocinium system can only be understood⁽⁶⁶⁾ in terms of specific solvation effects which are incompatible with the parallel solvation changes of these two substrates implicit in the redox potential assumption. The solvation of organometallic species should prove a most rewarding area for continued study, but it will be some time before the overall picture becomes as clear as in the more limited area of classical transition metal complexes considered in the present Review.     

Freezing and thawing porous media: experimental study with a dielectric capacitive method

A capacitive sensor-based apparatus has been used to study the ice/water phase change in consolidated porous media subjected to freezing and thawing. This technique relies on the dielectric properties of water, ice, air, and the mineral substrate in the radio-frequency range. It gives directly the freezing and thawing temperature depressions and indirectly provides an estimation of pore size distribution through the Gibbs–Thomson relation. It also holds good promise for evaluating the amount of liquid water in frozen porous media by combining drying and freezing tests. To cite this article: T. Fen-Chong, A. Fabbri, C. R. Mecanique 333 (2005).     

Crystalline Mean Curvature Flow of Convex Sets

We prove a local existence and uniqueness result of crystalline mean curvature flow starting from a compact convex admissible set in . This theorem can handle the facet breaking/bending phenomena, and can be generalized to any anisotropic mean curvature flow. The method provides also a generalized geometric evolution starting from any compact convex set, existing up to the extinction time, satisfying a comparison principle, and defining a continuous semigroup in time. We prove that, when the initial set is convex, our evolution coincides with the flat φ-curvature flow in the sense of Almgren-Taylor-Wang. As a by-product, it turns out that the flat φ-curvature flow starting from a compact convex set is unique.     

Experimental determination and prediction of methane hydrate stability in alcohols and electrolyte solutions

In petroleum exploration and production operations, gas hydrates pose serious flow assurance, economic and safety concerns. Thermodynamic inhibitors are widely used to reduce the risks associated with gas hydrate formation. In this communication, in order to establish the effects of salts and thermodynamic inhibitors on the locus of incipient hydrate–liquid water–vapour (H–L_W–V) curve, we report new experimental dissociation data for various quaternary systems, methane/water/thermodynamic inhibitor/salts for a pressure range of 6.89–29 MPa.