Photoreactive surfactants: a facile and clean route to oxide and metal nanoparticles in reverse micelles

A new class of photoreactive surfactants (PRSs) is presented here, consisting of amphiphiles that can also act as reagents in photochemical reactions. An example PRS is cobalt 2-ethylhexanoate (Co(EH)(2)), which forms reverse micelles (RMs) in a hydrocarbon solvent, as well as mixed reversed micelles with the standard surfactant Aerosol-OT (AOT). Small-angle neutron scattering (SANS) data show that mixed AOT/PRS RMs have a spherical structure and size similar to that of pure AOT micelles. Excitation of the ligand-to-metal charge transfer (LMCT) band in the PRSs promotes electron transfer from PRS to associated metal counterions, leading to the generation of metal and metal-oxide nanoparticles inside the RMs. This work presents proof of concept for employing PRSs as precursors to obtain nearly monodisperse inorganic nanoparticles: here both Co(3)O(4) and Bi nanoparticles have been synthesized at high metal concentration (10(-2) M) by simply irradiating the RMs. These results point toward a new approach of photoreactive self-assembly, which represents a clean and straightforward route to the generation of nanomaterials.     

Thiocyanate and nitrite analysis using miniaturised isotachophoresis on a planar polymer chip

A new method has been developed to improve the determination of thiocyanate using isotachophoresis. This method uses complexation with copper(II) as a mechanism for improving the separation of thiocyanate from chlorate and perchlorate. By using a pH of 3.25 the method can also be used to analyse nitrite. Separations were carried out using a miniaturised poly(methyl methacrylate) (PMMA) separation device. Linearity was observed from 1.25 to 75 mg dm(-3) with a correlation coefficient of 0.998 for both thiocyanate and nitrite. Limits of detection for these two species were calculated to be 0.8 mg dm(-3) and 0.9 mg dm(-3) respectively. The method was successfully applied to the analysis of these anions in a range of samples including explosive residues.     

The intermediate scattering function for lipid bilayer membranes: from nanometers to microns

A numerical scheme based upon established hydrodynamic and elastic considerations is introduced and used to predict the intermediate scattering function for lipid bilayer membranes. The predictions span multiple wavelength regimes, including those studied by dynamic light scattering (DLS; microns) and neutron spin-echo (NSE) spectroscopy (10-100 nm). The results validate a recent theory specific to the NSE regime and expose slight inaccuracies associated with the theoretical results available in the DLS regime. The assumptions that underlie both our numerical methods and the related theoretical predictions are reviewed in detail to explain when certain results can be applied to experiment and where caution must be exercised.     

Nickel complexes of a bis(benzimidazolin-2-ylidene)pyridine pincer ligand with four- and five-coordinate geometries

The four- and five-coordinate complexes [(CNC)NiX(2)] (X = Cl, Br, I), [(CNC)NiX]PF(6) (X = Cl, Br) and [(CNC)NiCl]Cl·H(2)O have been isolated, where CNC is the bis(N-butylbenzimidazolin-2-ylidene)-2,6-pyridine pincer ligand. A five-coordinate geometry is rare for this class of complex. Where amenable, the complexes have been structurally characterised by single crystal X-ray diffraction studies and in solution by NMR, UV-vis and MS studies. The five-coordinate dibromo complex [(CNC)NiBr(2)] is readily prepared on the gram-scale from the benzimidazolium salt precursor and Ni(OAc)(2)·4H(2)O in DMSO without the exclusion of air. Halide exchange and salt metathesis reactions using [(CNC)NiBr(2)] afford the other four- and five-coordinate complexes. [(CNC)NiBr(2)] displays very low solubility, and upon dissolution affords solutions of the four-coordinate [(CNC)NiBr](+). Factors that influence the formation of four- or five-coordinate complexes with this ligand class are discussed.     

Scaffold diversity of exemplified medicinal chemistry space

The scaffold diversity of 7 representative commercial and proprietary compound libraries is explored for the first time using both Murcko frameworks and Scaffold Trees. We show that Level 1 of the Scaffold Tree is useful for the characterization of scaffold diversity in compound libraries and offers advantages over the use of Murcko frameworks. This analysis also demonstrates that the majority of compounds in the libraries we analyzed contain only a small number of well represented scaffolds and that a high percentage of singleton scaffolds represent the remaining compounds. We use Tree Maps to clearly visualize the scaffold space of representative compound libraries, for example, to display highly populated scaffolds and clusters of structurally similar scaffolds. This study further highlights the need for diversification of compound libraries used in hit discovery by focusing library enrichment on the synthesis of compounds with novel or underrepresented scaffolds.     

Cycle extendability in graphs and digraphs

In 1990, Hendry conjectured that all chordal Hamiltonian graphs are cycle extendable, that is, the vertices of each non-Hamiltonian cycle are contained in a cycle of length one greater. Let A be a symmetric (0,1)-matrix with zero main diagonal such that A is the adjacency matrix of a chordal Hamiltonian graph. Hendry’s conjecture in this case is that every k×k principle submatrix of A that dominates a full cycle permutation k×k matrix is a principle submatrix of a (k+1)×(k+1) principle submatrix of A that dominates a (k+1)×(k+1) full cycle permutation matrix. This article generalizes the concept of cycle-extendability to S-extendable; that is, with S⊆{1,2,…,n} and G a graph on n vertices, G is S-extendable if the vertices of every non-Hamiltonian cycle are contained in a cycle length i greater, where i∈S. We investigate this concept in directed graphs and in particular tournaments, i.e., anti-symmetric matrices with zero main diagonal.     

The scalar Nevanlinna-Pick interpolation problem with boundary conditions

We show that if the Nevanlinna-Pick interpolation problem is solvable by a function mapping into a compact subset of the unit disc, then the problem remains solvable with the addition of any number of boundary interpolation conditions, provided the boundary interpolation values have modulus less than unity. We give new, inductive proofs of the Nevanlinna-Pick interpolation problem with any finite number of interpolation points in the interior and on the boundary of the domain of interpolation (the right half plane or unit disc), with function values and any finite number of derivatives specified. Our solutions are analytic on the closure of the domain of interpolation. Our proofs only require a minimum of matrix theory and operator theory. We also give new, straightforward algorithms for obtaining minimal H_∞ norm solutions. Finally, some numerical examples are given.     

A replaceable microreactor for on-line protein digestion in a two-dimensional capillary electrophoresis system with tandem mass spectrometry detection

We describe a two-dimensional capillary electrophoresis system that incorporates a replaceable enzymatic microreactor for on-line protein digestion. In this system, trypsin is immobilized on magnetic beads. At the start of each experiment, old beads are flushed to waste and replaced with a fresh plug of beads, which is captured by a pair of magnets at the distal tip of the first capillary. For analysis, proteins are separated in the first capillary. A fraction is then parked in the reactor to create peptides. Digested peptides are periodically transferred to the second capillary for separation; a fresh protein fraction is simultaneously moved to the reactor for digestion. An electrospray interface is used to introduce peptides into a mass spectrometer for analysis. This procedure is repeated for several dozen fractions under computer control. The system was demonstrated by the separation and digestion of insulin chain b oxidized and β-casein as model proteins.     

Ultrasensitive fluorescence-based methods for nucleic acid detection: towards amplification-free genetic analysis

Real time PCR is the mainstay of current nucleic acid assays, underpinning applications in forensic science, point-of-care diagnostics and detection of bioterrorism agents. Despite its broad utility, the search for new tests continues, inspired by second and third generation DNA sequencing technologies and fuelled by progress in single molecule fluorescence spectroscopy, nanotechnology and microfabrication. These new methods promise the direct detection of nucleic acids without the need for enzymatic amplification. In this feature article, we provide a chemist's perspective on this multidisciplinary area, introducing the concepts of single molecule detection then focussing on the selection of labels and probe chemistry suitable for generating a signal detectable by ultrasensitive fluorescence spectroscopy. Finally, we discuss the further developments that are required to incorporate these detection platforms into integrated 'sample-in-answer-out' instruments, capable of detecting many target sequences in a matter of minutes.